JP6664509B2 - Polyisocyanate composition, blocked polyisocyanate composition, hydrophilic polyisocyanate composition, coating composition, and coating film - Google Patents

Description

The present invention relates to a polyisocyanate composition, a blocked polyisocyanate composition, a hydrophilic polyisocyanate composition, a coating composition, and a coating film. The present application is filed with Japanese Patent Application No. 2006-203095 filed on October 14, 2016 in Japan, and filed with Japanese Patent Application No. 2006-203088 filed on October 14, 2016 in Japan. Japanese Patent Application No. 2006-20382, Japanese Patent Application No. 2006-203111 filed on October 14, 2016, Japanese Patent Application No. 2006-203090 filed on October 14, 2016, Japanese Patent Application No. Priority based on Japanese Patent Application No. 2006-203889 filed in Japan, Japanese Patent Application No. 2006-203097 filed on October 14, 2016 and Japanese Patent Application No. 2006-203803 filed on October 14, 2016 in Japan And its content is incorporated herein.

Conventionally, urethane coatings formed from polyurethane coatings have very good flexibility, chemical resistance and stain resistance. In particular, a coating film using a non-yellowing polyisocyanate obtained from an aliphatic diisocyanate represented by hexamethylene diisocyanate (hereinafter also referred to as HDI) as a curing agent is further excellent in weather resistance, and the demand thereof is increasing.

However, the problem of these aliphatic polyisocyanates is that the drying property is poor.
As a solution to this problem, a technique for increasing the number of isocyanate group functional groups of polyisocyanate is known. However, generally, when the number of isocyanate group functional groups is increased, the viscosity of the polyisocyanate increases, which makes handling difficult. There was a limit.

Therefore, a technique using a low-viscosity triisocyanate compound alone (for example, see Patent Documents 3 and 6 to 7), or a technique for isocyanating a part of the triisocyanate compound (for example, see Patent Document 8). Is disclosed. When these triisocyanate compounds are used, those satisfying a low viscosity and a certain degree of drying property have been obtained.

Further, in recent years, technical development for lowering the viscosity of polyisocyanate used as a curing agent has been actively carried out due to an increase in protection of the global environment. This is because the amount of the organic solvent used in the coating composition can be reduced by lowering the viscosity of the polyisocyanate (for example, see Patent Documents 1 and 5).
Also, a technique for maintaining the number of isocyanate group functional groups and reducing the viscosity has been disclosed (for example, see Patent Document 2).

On the other hand, there has been disclosed a technique for improving the problem of the appearance of a coating film (for example, bumps, armpits, etc.) (for example, see Patent Document 4).
Further, one of the performances required for the polyurethane coating film is resistance to rain streak contamination. In order to solve this problem, it is required to make the surface of the coating film hydrophilic. Since the silicate compound is added to the hardener to be used in order to make it hydrophilic, compatibility between the hardener and the silicate compound is important. A technique has been disclosed in which polyisocyanate using diisocyanate has improved compatibility with silicate (see, for example, Patent Document 9).

In recent years, with the increasing protection of the global environment, lowering the viscosity of polyisocyanate used as a curing agent and improving drying properties to enhance work efficiency have been required. I have. In particular, there is disclosed a technology in which an isocyanurate structure is used as a main skeleton and which can reduce viscosity and improve quick drying (see Patent Document 2).
Further, a technique using a low-viscosity triisocyanate compound is disclosed (for example, see Patent Document 14).

Further, in the field of architectural exterior paints, organic solvents having low polarity are strongly desired from the viewpoint of working environment. In particular, it is disclosed that polyisocyanates having an allophanate structure of a monoalcohol have low viscosity and excellent solubility in low-polarity organic solvents (see Patent Documents 10 and 11). Has achieved a task that cannot be achieved.

Further, as a technique using a low-viscosity triisocyanate compound, a technique of improving quick drying by blending with a triisocyanate (Patent Document 12), and a method of reducing the number of isocyanate structures by including a predetermined amount of a nurate structure and an allophanate structure of triisocyanate A technique of increasing the viscosity and drying quickly (Patent Document 8) has been disclosed, and further lowering the viscosity and improving the drying property have been achieved.

Also, from the aspect of global environmental protection, the development of water-based urethane coatings that use almost no solvent has been actively pursued. As a curing agent technology that has excellent performance in both solvent-based and water-based coatings, hydrophilic A technique has been disclosed in which the number of isocyanate groups is maintained without adding a group, and the viscosity is reduced, whereby the dispersion can be carried out in water and the durability of the obtained coating film is increased (Patent Document 13).

Japanese Patent No. 3055197 Japanese Patent No. 5178200 JP-B-63-15264 Japanese Patent No. 4037750 JP 05-222007 A JP-A-53-135931 JP-A-60-45661 JP-A-10-87782 JP 2006-348235 A Japanese Patent No. 5334361 Japanese Patent No. 3891934 JP-A-57-198761 JP-A-11-286649 JP-A-57-198760 JP 2008-024828 A

However, when the polyisocyanates disclosed in Patent Literatures 1 and 5 are used, the number of functional groups of the isocyanate group may be reduced, so that the drying property may be reduced.
Also, in the polyisocyanate disclosed in Patent Document 2, there is a case where further lowering the viscosity is desired.
Further, in the case of the polyisocyanate disclosed in Patent Documents 3-4, the adhesion to the base when forming a multilayer coating film may be insufficient.
As described above, the polyisocyanate is often used as a curing agent for a urethane coating film in a material for a multilayer coating film, and is required to have a low viscosity for improving the appearance, and is also required to have a drying property and a base. What has excellent adhesiveness has long been desired.
The present invention has been made in view of the above circumstances, and provides a polyisocyanate having a low viscosity and excellent coating properties such as quick-drying property, concealing property of a base, and adhesion to a base.

In addition, due to the labor saving of work and the demand for more durability, the polyisocyanate has a further improvement in drying property and forms a coating film with excellent acid resistance and hydrolysis resistance. It is required to be compatible with high polyols. Further, even under severe conditions, it is required that the coating film has high crack resistance.
However, in the triisocyanates and polyisocyanates disclosed in Patent Documents 3 and 6 to 8, it has been difficult to simultaneously reduce the viscosity and the above-mentioned requirements.
The present invention has been made in view of the above circumstances, has low viscosity, and has excellent compatibility with polar polyols, and has excellent crack resistance under conditions where temperature and humidity changes are repeated. Provided is a polyisocyanate composition capable of forming a coating film.

In addition, from the background of the need for further durability as well as labor saving of the work, polyisocyanate is required to further improve the drying property and to form a coating film having excellent hardness and water resistance.
However, in the triisocyanate and polyisocyanate disclosed in Patent Literatures 3 and 6 to 8, it has been difficult to simultaneously satisfy the above requirements.
The present invention has been made in view of the above circumstances, and provides a polyisocyanate composition capable of forming a coating film having excellent drying properties, hardness, and water resistance.

In addition, from the background of labor demands and increased durability requirements, polyisocyanates are required to have further improved drying properties and improved adhesion to substrates. However, even with the triisocyanates and polyisocyanates disclosed in Patent Documents 3 and 6 to 8, it has been difficult to achieve both dryness and adhesion to a substrate.
The present invention has been made in view of the above circumstances, has good drying properties, and forms a coating film having good adhesion to a substrate even in an environment with a change in temperature and humidity. It is an object of the present invention to provide a polyisocyanate composition, a coating composition and a coating film which can be used.

In addition, as described above, compatibility with silicate compounds has been demanded for improvement of stain resistance to rain streaks. However, in the polyisocyanate and triisocyanate compounds disclosed in Patent Documents 1, 3, 5 to 8, silicate is used. It was difficult to achieve compatibility with the compound.
Further, the polyisocyanate composition disclosed in Patent Document 9 has a drawback that although the compatibility with the silicate compound is improved, the drying property is poor.
The present invention has been made in view of the above circumstances, and has a low viscosity, a polyisocyanate composition having excellent silicate compatibility, a coating composition having good drying properties and recoat adhesion, and abrasion resistance. Provides excellent coatings.

In addition, due to the labor saving of work and the demand for more durability, the polyisocyanate has a further improvement in drying property and forms a coating film with excellent acid resistance and hydrolysis resistance. It is required to be compatible with high polyols. However, in the triisocyanates and polyisocyanates disclosed in Patent Documents 3 and 6 to 8, it has been difficult to simultaneously reduce the viscosity and satisfy the above-mentioned requirements.
The present invention provides a polyisocyanate composition having a low viscosity, a fast drying property, and excellent compatibility with a polar polyol.

Further, the polyisocyanates disclosed in Patent Documents 10 and 11 have a problem that when the number of functional groups is reduced to reduce the viscosity, the drying property is reduced, and when the number of functional groups is increased, the viscosity is increased. It was difficult to simultaneously satisfy the low viscosity.
In the polyisocyanates disclosed in Patent Literatures 8 and 12, although the drying property is improved while maintaining the low viscosity, it is not easy to achieve both at a high level, and the low viscosity is environmentally friendly. Attempts to dissolve in polar organic solvents did not provide sufficient solubility.
Furthermore, the polyisocyanates described in Patent Documents 2, 8, and 10 to 12 are used in a solvent system, and it has been difficult to disperse the polyisocyanate in water and use it as a curing agent for water-based paints. Patent Document 13 discloses a technique of using as a curing agent dispersed in water without reducing the number of isocyanate groups, but the time in which the state of dispersion in water can be maintained is short, and it is used for ordinary paints. It was difficult.
In the field of architectural exterior paint and automotive interior / exterior paint, etc., the curing agent of the paint has low viscosity to reduce the amount of solvent used, has quick drying property to shorten the coating time, and from the viewpoint of the working environment It is desirable to be able to dissolve in a low-polarity organic solvent or to be able to disperse in water so that it can be used in a water-based paint that can greatly reduce the amount of a solvent. . However, it has been difficult to solve these requirements simultaneously.

  The present invention has been made in view of the above circumstances, has a low viscosity, and fast drying, excellent solubility in a low-polarity organic solvent, so that it is suitable for a curing agent for a solvent-based paint, and furthermore, is easy to water. The present invention provides a polyisocyanate which can be used as a curing agent for a water-based paint because it can be dispersed in water.

Further, when the polyisocyanate disclosed in Patent Document 2 is used, further lowering of the viscosity may be required, and when the polyisocyanate disclosed in Patent Document 14 is used, the drying property may be reduced. .
Further, in the polyisocyanates disclosed in Patent Literatures 11 and 15, drying properties may be reduced due to a decrease in the number of functional groups.
For example, in the field of architectural exterior paints, the problems of low viscosity for reducing the amount of solvent used, quick drying for shortening the coating time, and solubility in low-polarity organic solvents from the viewpoint of the working environment can be satisfied. There is a strong need for a curing agent. However, it has been difficult to solve these requirements simultaneously.
The present invention has been made in view of the above circumstances, and provides a polyisocyanate having low viscosity, quick drying, and excellent solubility in a low polar organic solvent.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a polyisocyanate composition having a specific structure can achieve the above object, and have accomplished the present invention.
That is, the present invention includes the following aspects. [1] A polyisocyanate composition containing a polyisocyanate compound represented by the general formula (I), (II), (III) or (IV).

［一般式（Ｉ）、（ＩＩ）、（ＩＩＩ）および（ＩＶ）中、複数あるＲ^１１、Ｒ^２１、Ｒ^３１およびＲ^４１は、それぞれ独立に、有機基であり、複数あるＲ ^１１ 、Ｒ ^３１ およびＲ ^４１ のうち少なくとも１つは一般式（Ｖ）または（ＶＩ）で表される基であり、複数あるＲ ^２１ のうち少なくとも１つは一般式（Ｖ）で表される基である。複数あるＲ^１１、Ｒ^２１、Ｒ^３１およびＲ^４１は、それぞれ同一であってもよく異なっていてもよい。一般式（ＩＩＩ）中、Ｒ^３２は、１価以上のアルコールから１つのヒドロキシ基を除去した残基である。」

[In general formulas (I), (II), (III) and (IV), a plurality of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ are each independently an organic group, and a plurality of R ¹¹ , R ^At least one of R ³¹ and R ⁴¹ is a group represented by formula (V) or (VI), and at least one of a plurality of R ²¹ is a group represented by formula (V). A plurality of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ may be the same or different. In the general formula (III), R ³² is a residue obtained by removing one hydroxy group from a monohydric or higher alcohol. "

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

［一般式（ＶＩ）中、Ｙ^２はエステル構造を含む炭素数１〜２０の２価の炭化水素基である。波線は結合手を意味する。］［２］一般式（Ｉ）および一般式（ＩＩ）で表されるポリイソシアネート化合物を含む、［１］に記載のポリイソシアネート組成物。

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond. [2] The polyisocyanate composition according to [1], comprising a polyisocyanate compound represented by the general formula (I) and the general formula (II).

［一般式（Ｉ）および一般式（ＩＩ）中、複数あるＲ^１１およびＲ^２１は、それぞれ独立に、有機基であり、複数あるＲ^１１およびＲ^２１のうち少なくとも１つは一般式（Ｖ）で表される基である。複数あるＲ^１１およびＲ^２１は、それぞれ同一であってもよく異なっていてもよい。］

[In the general formulas (I) and (II), a plurality of R ¹¹ and R ²¹ are each independently an organic group, and at least one of the plurality of R ¹¹ and R ²¹ is a group represented by the general formula (V) Is a group represented by A plurality of R ¹¹ and R ²¹ may be the same or different. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］［３］前記一般式（Ｉ）および前記一般式（ＩＩ）で表されるポリイソシアネート化合物を含み、

イミノオキサジアジンジオン構造とイソシアヌレート構造とのモル比率が、０．０１以上１．５以下である、［２］に記載のポリイソシアネート組成物。［４］一般式（Ｖ）−１で表されるトリイソシアネートをさらに含む、［２］または［３］に記載のポリイソシアネート組成物。

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. [3] including a polyisocyanate compound represented by the general formula (I) and the general formula (II),

The polyisocyanate composition according to [2], wherein the molar ratio between the iminooxadiazinedione structure and the isocyanurate structure is 0.01 or more and 1.5 or less. [4] The polyisocyanate composition according to [2] or [3], further comprising a triisocyanate represented by the general formula (V) -1.

［一般式（Ｖ）−１中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。］［５］前記一般式（ＩＩ）で表されるポリイソシアネート化合物を含み、ポリイソシアネート組成物のＮＣＯ％から算出される、理論反応率が４７％以下である、［２］〜［４］のいずれか一項に記載のポリイソシアネート組成物。
［６］前記一般式（ＩＩ）で表されるポリイソシアネート化合物を含み、ポリイソシアネート組成物のＮＣＯ％から算出される、理論反応率が９５％以上１５０％以下である、［２］〜［４］のいずれか一項に記載のポリイソシアネート組成物。
［７］前記一般式（ＩＩ）で示されるポリイソシアネート化合物（Ａ）と、前記一般式（Ｖ）−１で示されるトリイソシアネート化合物（Ｂ）とを含む、ポリイソシアネート組成物であって、

ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定で得られる、前記ポリイソシアネート化合物（Ａ）の数平均分子量のピーク面積（Ａ）と、前記トリイソシアネート化合物（Ｂ）の数平均分子量のピーク面積（Ｂ）と、の面積比率（（Ａ）／［（Ａ）＋（Ｂ）］）が０．８以上１未満である、［４］に記載のポリイソシアネート組成物。［８］前記一般式（ＩＩ）中のＲ^２１のすべてが前記一般式（Ｖ）で示されるトリイソシアネートであるモノマー３量体を化合物（Ｃ）とした時、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定で得られる、前記ポリイソシアネート化合物（Ａ）の数平均分子量のピーク面積（Ａ）と、前記トリイソシアネート化合物（Ｂ）の数平均分子量のピーク面積（Ｂ）と、前記化合物（Ｃ）の数平均分子量のピーク面積（Ｃ）との面積比率（（Ｃ）／［（Ａ）＋（Ｂ）］）が０．３以上１未満である、［７］に記載のポリイソシアネート組成物。
［９］イソシアネート基官能価が４以上１２以下である、［７］または［８］に記載のポリイソシアネート組成物。
［１０］一般式（ＩＩ）および一般式（ＩＩＩ）で表されるポリイソシアネート化合物を含み、イソシアヌレート構造とアロファネート構造とのモル比が１００／０．１〜１００／１５である、［１］に記載のポリイソシアネート組成物。

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. [5] The composition according to any of [2] to [4], comprising a polyisocyanate compound represented by the general formula (II), and having a theoretical conversion of 47% or less, calculated from the NCO% of the polyisocyanate composition. The polyisocyanate composition according to claim 1.
[6] The polyisocyanate compound represented by the general formula (II), wherein the theoretical conversion calculated from the NCO% of the polyisocyanate composition is 95% or more and 150% or less, [2] to [4] ] The polyisocyanate composition of any one of the above.
[7] A polyisocyanate composition comprising a polyisocyanate compound (A) represented by the general formula (II) and a triisocyanate compound (B) represented by the general formula (V) -1;

The peak area (A) of the number average molecular weight of the polyisocyanate compound (A) and the peak area (B) of the number average molecular weight of the triisocyanate compound (B) obtained by gel permeation chromatography (GPC) measurement. The polyisocyanate composition according to [4], wherein the area ratio ((A) / [(A) + (B)]) is 0.8 or more and less than 1. [8] When a monomer trimer in which all of R ^{21 in} the general formula (II) is a triisocyanate represented by the general formula (V) is a compound (C), gel permeation chromatography (GPC) The peak area (A) of the number average molecular weight of the polyisocyanate compound (A), the peak area (B) of the number average molecular weight of the triisocyanate compound (B), and the number of the compound (C) obtained by the measurement. The polyisocyanate composition according to [7], wherein the area ratio ((C) / [(A) + (B)]) of the average molecular weight to the peak area (C) is 0.3 or more and less than 1.
[9] The polyisocyanate composition according to [7] or [8], wherein the isocyanate group functionality is 4 or more and 12 or less.
[10] The polyisocyanate compound represented by the general formula (II) or (III), wherein the molar ratio of the isocyanurate structure to the allophanate structure is 100 / 0.1 to 100/15, [1]. The polyisocyanate composition according to the above.

［一般式（ＩＩ）および一般式（ＩＩＩ）中、複数あるＲ^２１およびＲ^３１は、それぞれ独立に、有機基であり、複数あるＲ^２１およびＲ^３１のうち少なくとも１つは一般式（Ｖ）で表される基である。複数あるＲ^２１およびＲ^３１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^３２は、１価以上のアルコールから１つのヒドロキシ基を除去した残基である。］

[In the general formulas (II) and (III), a plurality of R ²¹ and R ³¹ are each independently an organic group, and at least one of the plurality of R ²¹ and R ³¹ is a group represented by the general formula (V) Is a group represented by A plurality of R ²¹ and R ³¹ may be the same or different. R ³² is a residue obtained by removing one hydroxy group from a monovalent or higher alcohol. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］
［１１］一般式（Ｖ）−１で表されるトリイソシアネートをさらに含む、［１０］に記載のポリイソシアネート組成物。

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]
[11] The polyisocyanate composition according to [10], further comprising a triisocyanate represented by the general formula (V) -1.

［一般式（Ｖ）−１中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。］［１２］一般式（ＩＩ）および一般式（ＩＶ）で表されるポリイソシアネート化合物を含み、イソシアヌレート構造とウレトジオン構造とのモル比が１００／０．１〜１００／１００である、［１］に記載のポリイソシアネート組成物。

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. [12] The polyisocyanate compound represented by the general formula (II) or (IV), wherein the molar ratio between the isocyanurate structure and the uretdione structure is 100 / 0.1 to 100/100. ] The polyisocyanate composition as described in [1].

［一般式（ＩＩ）および（ＩＶ）中、複数あるＲ^２１およびＲ^４１は、それぞれ独立に、有機基であり、複数あるＲ^２１およびＲ^４１のうち少なくとも１つは一般式（Ｖ）で表される基である。複数あるＲ^２１およびＲ^４１は、それぞれ同一であってもよく異なっていてもよい。」

[In the general formulas (II) and (IV), a plurality of R ²¹ and R ⁴¹ are each independently an organic group, and at least one of the plurality of R ²¹ and R ⁴¹ is represented by the general formula (V). It is a group to be performed. A plurality of R ²¹ and R ⁴¹ may be the same or different. "

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］［１３］一般式（Ｖ）−１で表されるトリイソシアネートをさらに含む、［１２］に記載のポリイソシアネート組成物。

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. [13] The polyisocyanate composition according to [12], further comprising a triisocyanate represented by the general formula (V) -1.

［一般式（Ｖ）−１中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。］
［１４］一般式（ＩＩ）で表されるポリイソシアネート化合物を含み、
ヘキサメチレンジイソシアネートから誘導されるポリイソシアネートと１級アルコールとの反応速度（Ｖ ^ｈ ）に対する、ポリイソシアネート組成物と１級アルコールとの反応速度（Ｖ ^ｐ ）の比（Ｖ ^ｈ ／Ｖ ^ｐ ）が、５以上１３未満である、ポリイソシアネート組成物。

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]
[14] the general formula polyisocyanate compound represented by (II) seen including,
The ratio (V ^h / V ^p ) of the reaction rate (V ^p ) between the polyisocyanate composition and the primary alcohol to the reaction rate (V ^h ) between the polyisocyanate derived from hexamethylene diisocyanate and the primary alcohol , The polyisocyanate composition , which is 5 or more and less than 13 .

［一般式（ＩＩ）中、Ｒ^２１は有機基である。複数あるＲ^２１のうち少なくとも１つは、一般式（Ｖ）で表される基、または一般式（ＶＩ）で表される基である。複数あるＲ^２１は、それぞれ同一であってもよく異なっていてもよい。］

[In the general formula (II), R ²¹ is an organic group. At least one of the plurality of R ²¹ is a group represented by the general formula (V) or a group represented by the general formula (VI). A plurality of R ²¹ may be the same or different. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、エステル構造および／またはエーテル構造を含んでいる炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］

[In the general formula (V), a plurality of Y ¹ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms and containing an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

［一般式（ＶＩ）中、Ｙ^２はエステル構造を含む炭素数１〜２０の２価の炭化水素基である。波線は結合手を意味する。］
［１５］一般式（Ｖ）−１で表されるトリイソシアネートまたは一般式（ＶＩ）−１で示されるジイソシアネートをさらに含む、［１４］に記載のポリイソシアネート組成物。

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond . ]
[ 15 ] The polyisocyanate composition according to [14] , further comprising a triisocyanate represented by the general formula (V) -1 or a diisocyanate represented by the general formula (VI) -1.

［一般式（Ｖ）−１中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。］

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

［一般式（ＶＩ）−１中、Ｙ^２はエステル構造を含んでいてもよい炭素数１〜２０の２価の炭化水素基である。］
［１６］一般式（ＩＩＩ）で示されるポリイソシアネート化合物を含むポリイソシアネート組成物であって、
該ポリイソシアネート組成物に含まれるイソシアネート基、アロファネート構造、イソシアヌレート構造、ウレトジオン構造、イミノオキサジアジンジオン構造、ウレタン構造、およびビュレット構造に含まれる窒素元素の総数に対して、該アロファネート構造に含まれる窒素元素（ただし、Ｒ^３１、Ｒ^３２に含まれる窒素元素を除く）の数が１．５％以上６０％以下である［１］に記載のポリイソシアネート組成物。

[In general formula (VI) -1, Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ester structure. ]
[ 16 ] A polyisocyanate composition containing a polyisocyanate compound represented by the general formula (III),
The isocyanate group contained in the polyisocyanate composition, allophanate structure, isocyanurate structure, uretdione structure, iminooxadiazinedione structure, urethane structure, and the total number of nitrogen elements contained in the burette structure included in the allophanate structure The polyisocyanate composition according to [1], wherein the number of nitrogen elements (excluding nitrogen elements contained in R ³¹ and R ³² ) is 1.5% or more and 60% or less.

［一般式（ＩＩＩ）中、Ｒ^３１は有機基である。複数あるＲ^３１のうち少なくとも１つは、一般式（Ｖ）で示される基であり、Ｒ^３２は１価以上のアルコールのヒドロキシル基を除去した残基である。］

[In the general formula (III), R ³¹ is an organic group. At least one of the plurality of R ³¹ is a group represented by the general formula (V), and R ³² is a residue obtained by removing a hydroxyl group of a monohydric or higher alcohol. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］
［１７］前記アロファネート構造に含まれるＲ^３２が、２価以上のアルコールのヒドロキシル基を除去した残基である、請求項１６に記載のポリイソシアネート組成物。
［１８］前記アロファネート構造に含まれるＲ^３２が、炭素数３〜５０である１価以上のアルコールのヒドロキシル基を除去した残基である、［１６］または［１７］に記載のポリイソシアネート組成物。
［１９］一般式（ＩＩＩ）で表されるポリイソシアネート化合物を含む、［１］に記載のポリイソシアネート組成物。

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]
[17] R ³² contained in the allophanate structure is a residue obtained by removing the divalent or more hydroxyl groups of the alcohol, polyisocyanate composition according to claim 16.
[ 18 ] The polyisocyanate composition according to [ 16 ] or [ 17 ], wherein R ³² contained in the allophanate structure is a residue obtained by removing a hydroxyl group of a monohydric or higher alcohol having 3 to 50 carbon atoms. .
[ 19 ] The polyisocyanate composition according to [1], comprising a polyisocyanate compound represented by the general formula (III).

［一般式（ＩＩＩ）中、複数あるＲ^３１は、それぞれ独立に、有機基であり、複数あるＲ^３１のうち少なくとも１つは一般式（Ｖ）で表される基、または一般式（ＶＩ）で表される基である。複数あるＲ^３１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^３２は、１価以上のアルコールから１つのヒドロキシ基を除去した残基である。］

[In general formula (III), a plurality of R ³¹ are each independently an organic group, and at least one of the plurality of R ³¹ is a group represented by general formula (V) or a general formula (VI) Is a group represented by A plurality of R ³¹ may be the same or different. R ³² is a residue obtained by removing one hydroxy group from a monovalent or higher alcohol. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

［一般式（ＶＩ）中、Ｙ^２はエステル構造を含む炭素数１〜２０の２価の炭化水素基である。波線は結合手を意味する。］
［２０］アロファネート構造、ウレトジオン構造、イミノオキサジアジンジオン構造、イソシアヌレート構造、ウレタン構造、およびビュレット構造の各モル比率をａ、ｂ、ｃ、ｄ、ｅ、およびｆとしたとき、アロファネート構造のモル比率（ａ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ））が、０．０２以上０．９５以下である、［１９］に記載のポリイソシアネート組成物。
［２１］ヘキサメチレンジイソシアネートから誘導されるポリイソシアネートと１級アルコールとの反応速度（Ｖ^ｈ）に対する、ポリイソシアネート組成物と１級アルコールとの反応速度（Ｖ^ｐ）の比（Ｖ^ｈ／Ｖ^ｐ）が、５以上１３未満である、［１９］または［２０］に記載のポリイソシアネート組成物。
［２２］一般式（Ｖ）−１で表されるトリイソシアネートまたは一般式（ＶＩ）−１で示されるジイソシアネートをさらに含む、［１９］〜［２１］のいずれか一項に記載のポリイソシアネート組成物。

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond. ]
[ 20 ] When allophanate structure, uretdione structure, iminooxadiazinedione structure, isocyanurate structure, urethane structure, and buret structure are represented by a, b, c, d, e, and f, respectively, the allophanate structure The polyisocyanate composition according to [ 19 ], wherein the molar ratio (a / (a + b + c + d + e + f)) is 0.02 or more and 0.95 or less.
[21] against the rate of reaction of a polyisocyanate with primary alcohols derived from hexamethylene diisocyanate ^{(V h),} the polyisocyanate composition and the ratio ^(V h / V ^p of the reaction rate of the primary alcohol ^{(V p)} ) Is 5 or more and less than 13, wherein the polyisocyanate composition according to [ 19 ] or [ 20 ].
[22] The polyisocyanate composition according to any one of [ 19 ] to [ 21 ], further including a triisocyanate represented by the general formula (V) -1 or a diisocyanate represented by the general formula (VI) -1. object.

［一般式（Ｖ）−１中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。］

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

［一般式（ＶＩ）−１中、Ｙ^２はエステル構造を含んでいてもよい炭素数１〜２０の２価の炭化水素基である。］
［２３］［１］〜［２２］のいずれか一項に記載のポリイソシアネート組成物が含有する前記一般式（Ｉ）、（ＩＩ）、（ＩＩＩ）または（ＩＶ）で表されるポリイソシアネート化合物の、イソシアネート基の少なくとも一部がブロック剤で保護された、ブロックポリイソシアネート組成物。
［２４］［１］〜［２３］のいずれか一項に記載のポリイソシアネート組成物が含有する前記一般式（Ｉ）、（ＩＩ）、（ＩＩＩ）または（ＩＶ）で表されるポリイソシアネート化合物の、イソシアネート基の少なくとも一部に親水性基が付加された、親水性ポリイソシアネート組成物。
［２５］［２３］に記載のブロックポリイソシアネート組成物が含有する前記一般式（Ｉ）、（ＩＩ）、（ＩＩＩ）または（ＶＩ）で表されるポリイソシアネート化合物の、イソシアネート基の少なくとも一部に親水性基が付加された、親水性ポリイソシアネート組成物。
［２６］［１］〜［２２］のいずれか一項に記載のポリイソシアネート組成物と、ポリオールとを含む、塗料組成物。
［２７］［２３］に記載のブロックポリイソシアネート組成物と、ポリオールとを含む、塗料組成物。
［２８］［２４］または［２５］に記載の親水性ポリイソシアネート組成物と、ポリオールとを含む、塗料組成物。
［２９］［２６］〜［２８］のいずれか一項に記載の塗料組成物を硬化した塗膜。
［３０］水と、水に分散した［１６］〜［１９］のいずれかに記載のポリイソシアネート組成物、とを含む、水分散体。
［３１］水と、［２３］に記載のブロックポリイソシアネート組成物、とを含む、水分散体。
［３２］水と、［２３］または［２４］に記載の親水性ポリイソシアネート組成物、とを含む、水分散体。

[In general formula (VI) -1, Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ester structure. ]
[ 23 ] The polyisocyanate compound represented by the general formula (I), (II), (III) or (IV) contained in the polyisocyanate composition according to any one of [1] to [ 22 ]. The blocked polyisocyanate composition, wherein at least a part of the isocyanate group is protected by a blocking agent.
[ 24 ] The polyisocyanate compound represented by the general formula (I), (II), (III) or (IV) contained in the polyisocyanate composition according to any one of [1] to [ 23 ]. The hydrophilic polyisocyanate composition wherein a hydrophilic group is added to at least a part of the isocyanate group.
[ 25 ] At least a part of the isocyanate group of the polyisocyanate compound represented by the general formula (I), (II), (III) or (VI) contained in the blocked polyisocyanate composition according to [ 23 ]. A hydrophilic polyisocyanate composition, wherein a hydrophilic group is added to the polyisocyanate.
[ 26 ] A coating composition comprising the polyisocyanate composition according to any one of [1] to [ 22 ] and a polyol.
[ 27 ] A coating composition comprising the blocked polyisocyanate composition according to [ 23 ] and a polyol.
[ 28 ] A coating composition comprising the hydrophilic polyisocyanate composition according to [ 24 ] or [ 25 ], and a polyol.
[ 29 ] A coating film obtained by curing the coating composition according to any one of [ 26 ] to [ 28 ].
[ 30 ] An aqueous dispersion comprising water and the polyisocyanate composition according to any one of [ 16 ] to [ 19 ] dispersed in water.
[ 31 ] An aqueous dispersion comprising water and the blocked polyisocyanate composition according to [ 23 ].
[ 32 ] An aqueous dispersion comprising water and the hydrophilic polyisocyanate composition according to [23] or [24] .

  According to the present invention, it is possible to provide a polyisocyanate composition having a low viscosity and excellent in properties of a coating film such as quick-drying property, concealing property of a base, and adhesion to a base.

  According to the present invention, a polyisocyanate composition that has a low viscosity, has excellent compatibility with polar polyols, and is capable of forming a coating film having excellent crack resistance under conditions of temperature change, humidity change, and UV exposure. Can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the polyisocyanate composition which is excellent in drying property, and which can form a coating film excellent in hardness and water resistance can be provided.

  According to the present invention, there is provided a polyisocyanate composition which has good drying properties, and can form a coating film having good adhesion to a substrate even in an environment having a change in temperature and a change in humidity. be able to.

  According to the present invention, a polyisocyanate composition having low viscosity and excellent compatibility with silicate can be provided. Further, the coating composition using the polyisocyanate composition according to the present invention has excellent drying properties and recoat adhesion. Furthermore, the coating film obtained from the above coating composition has good scratch resistance.

  According to the present invention, it is possible to provide a polyisocyanate composition having a low viscosity and excellent in quick-drying property. Further, the coating composition using the polyisocyanate composition according to the present invention has excellent drying properties and substrate adhesion.

  According to the present invention, it is possible to provide a polyisocyanate composition having a low viscosity, a fast drying property, and an excellent compatibility with a polar polyol.

  According to the present invention, dissolving in a low-polarity solvent, can be compatible with quick-drying, and, since the viscosity is low, the amount of the solvent can be reduced, furthermore, the curing agent of the water-based paint by dispersing in water Can be provided.

  According to the present invention, it is possible to provide a polyisocyanate composition having low viscosity, quick drying, and excellent solubility in a low-polarity organic solvent.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. The following embodiments for carrying out the present invention are exemplifications for describing the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the invention.

In this specification, “polyisocyanate” refers to a polymer in which a plurality of monomers having one or more isocyanate groups (—NCO) are bonded.
As used herein, “polyol” refers to a compound having two or more hydroxy groups (—OH).

<Polyisocyanate composition>
[First Embodiment]

The polyisocyanate composition of the first embodiment of the present invention contains a polyisocyanate compound represented by the general formula (I), (II), (III) or (IV).

［一般式（Ｉ）、（ＩＩ）、（ＩＩＩ）および（ＩＶ）中、複数あるＲ^１１、Ｒ^２１、Ｒ^３１およびＲ^４１は、それぞれ独立に、有機基であり、複数あるＲ^１１、Ｒ^２１、Ｒ^３１およびＲ^４１のうち少なくとも１つは一般式（Ｖ）または（ＶＩ）で表される基である。複数あるＲ^１１、Ｒ^２１、Ｒ^３１およびＲ^４１は、それぞれ同一であってもよく異なっていてもよい。一般式（ＩＩＩ）中、Ｒ^３２は、１価以上のアルコールから１つのヒドロキシ基を除去した残基である。」

[In general formulas (I), (II), (III) and (IV), a plurality of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ are each independently an organic group, and a plurality of R ¹¹ , R ^At least one of ²¹ , R ³¹ and R ⁴¹ is a group represented by formula (V) or (VI). A plurality of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ may be the same or different. In the general formula (III), R ³² is a residue obtained by removing one hydroxy group from a monohydric or higher alcohol. "

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

［一般式（ＶＩ）中、Ｙ^２はエステル構造を含む炭素数１〜２０の２価の炭化水素基である。波線は結合手を意味する。］

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond. ]

[1-1 Embodiment]

The polyisocyanate composition of Embodiment 1-1 of the present invention contains a polyisocyanate compound represented by the general formula (I) or the general formula (II).

［一般式（Ｉ）および（ＩＩ）中、複数あるＲ^１１およびＲ^２１は、それぞれ独立に、有機基であり、複数あるＲ^１１およびＲ^２１のうち少なくとも１つは一般式（Ｖ）で表される基である。複数あるＲ^１１およびＲ^２１は、それぞれ同一であってもよく異なっていてもよい。」

[In general formulas (I) and (II), a plurality of R ¹¹ and R ²¹ are each independently an organic group, and at least one of the plurality of R ¹¹ and R ²¹ is represented by a general formula (V). It is a group to be performed. A plurality of R ¹¹ and R ²¹ may be the same or different. "

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］
以下、一般式（Ｉ）、一般式（ＩＩ）、および一般式（Ｖ）について説明する。

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]
Hereinafter, the general formula (I), the general formula (II), and the general formula (V) will be described.

-General formula (I)

一般式（Ｉ）で表されるポリイソシアネート化合物は、イミノオキサジアジンジオン構造を有する。イミノオキサジアジンジオン構造はイソシアネートモノマー３分子からなるポリイソシアネートである。

The polyisocyanate compound represented by the general formula (I) has an iminooxadiazinedione structure. The iminooxadiazinedione structure is a polyisocyanate composed of three isocyanate monomer molecules.

[R ¹¹ ]

In the general formula (I), a plurality of R ¹¹ are each independently an organic group. A plurality of R ¹¹ may be the same or different.
In the first 1-1 embodiment, of the three R ^11, at least one is a group represented by the general formula (V), groups in which two R ¹¹ is represented by the general formula (V) It is more preferable that all three R ¹¹ are groups represented by the above general formula (V).

Examples of the group other than the group represented by the general formula (III) in R ¹¹ include, for example, tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,2,4 -Trimethylhexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate (MPDI), 1,3-bis (isocyanatomethyl) -cyclohexane (1,3-H6-XDI), 3 (4) -Isocyanatomethyl-1-methyl-cyclohexylisoanate (IMCI); isophorone diisocyanate (IPDI), bis (isocyanatomethyl) -norbornane (NBDI), 1,3-bis (isocyanatomethyl) -benzene, 1, 3-bis (2-isocyanatopropyl-2) benzene And a residue obtained by removing one isocyanate group from 4,4′-dicyclohexylmethane diisocyanate (H12MDI).

-General formula (II)

一般式（ＩＩ）で表されるポリイソシアネート化合物は、イソシアヌレート構造を有する。イソシアヌレート構造はイソシアネートモノマー３分子からなるポリイソシアネートである。

The polyisocyanate compound represented by the general formula (II) has an isocyanurate structure. The isocyanurate structure is a polyisocyanate composed of three isocyanate monomer molecules.

[R ²¹ ]

In the general formula (II), a plurality of R ²¹ are each independently an organic group. A plurality of R ²¹ may be the same or different.
In the first 1-1 embodiment, of the three R ^21, at least one is a group represented by the general formula (V), groups in which two R ²¹ is represented by the general formula (V) It is more preferable that all three R ²¹ are groups represented by the above general formula (V).

Examples of the group other than the group represented by the general formula (V) in R ²¹ include, for example, the same groups as those exemplified in the above-described “• General formula (I)”.・ General formula (V)

[Y ¹ ]

In the general formula (V), a plurality of Y ¹ are each independently a single bond or a carbon which may contain an ester structure [—C (＝ O) —O—] and / or an ether structure (—O—). It is a divalent hydrocarbon group of the formulas 1 to 20. A plurality of Y ¹ may be the same or different.
Examples of the divalent hydrocarbon group having ester structure and / or carbon atoms which may contain an ether structure _{1~20, - (CH 2) n1} -X- (CH 2) n2 - group represented by (n1 and n2 Are each independently an integer from 0 to 10. However, both n1 and n2 are not 0. X is an ester group or an ether group.
When it is desired to increase the reaction rate, X is preferably an ester group.
n1 and n2 are preferably from 0 to 4, more preferably from 0 to 2. As a combination of n1 and n2, for example, a combination of n1 = 0 and n2 = 2, and a combination of n1 = 2 and n2 = 2 are preferable.

[ ^R51 ]

R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group for R ⁵¹ is not particularly limited, and includes an alkyl group, an alkenyl group, an alkynyl group, and the like. As R ⁵¹ , a hydrogen atom is preferable.

It is preferable that the molecular weight of the triisocyanate that is the base of the group represented by the general formula (V) in the 1-1 embodiment is from 139 to 1,000.
The lower limit of the molecular weight is preferably 150 or more, more preferably 180 or more, and particularly preferably 200 or more. The upper limit of the molecular weight is preferably 800 or less, more preferably 600 or less, and particularly preferably 400 or less. When the molecular weight is equal to or more than the above lower limit, crystallinity is easily suppressed. In addition, when the molecular weight is equal to or less than the above upper limit, lower viscosity can be easily achieved.

In order to reduce the viscosity of the triisocyanate that is the source of the group represented by the general formula (V) in the 1-1 embodiment, a plurality of hydrocarbon groups in Y ³¹ are an aliphatic group and / or an aromatic group. It is preferable to have Also, R ⁵¹ is preferably hydrogen.
In addition, it is preferable that a plurality of Y ¹ be composed of only a hydrocarbon group.
Further, in order to improve the weather resistance when used as a curing agent of the coating composition, but preferably the hydrocarbon group in the plurality of Y ¹ is an aliphatic group or an alicyclic group.
Separately, in order to maintain heat resistance, at least one of the plurality of Y ¹ preferably has an ester group.
Further, in order to maintain hydrolysis resistance, at least one of the plurality of Y ¹ preferably has a hydrocarbon group containing an ether structure or a hydrocarbon group.

Examples of the triisocyanate that is a source of the group represented by the general formula (V) in the 1-1 embodiment include 4-isocyanatomethyl-1,8-octaphthalate disclosed in JP-B-63-15264. Methylene diisocyanate (hereinafter sometimes referred to as “NTI”, molecular weight 251), 1,3,6-hexamethylene triisocyanate (hereinafter referred to as “HTI”) disclosed in JP-A-57-198760. Bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter referred to as GTI, molecular weight 311) disclosed in JP-B-4-1033, JP-A-53-135931. Lysine triisocyanate (hereinafter, referred to as LTI, molecular weight 267) and the like.
Among these, NTI, GTI or LTI is preferable, NTI or LTI is more preferable, and LTI is particularly preferable from the viewpoint of further improving the reactivity of the isocyanate group.

The triisocyanate serving as the base of the group represented by the general formula (V) in the 1-1 embodiment can be obtained by isocyanating an amino acid derivative or an amine such as an etheramine or an alkyltriamine. As the amino acid derivative, for example, 2,5-diaminovaleric acid, 2,6-diaminohexanoic acid, aspartic acid, glutamic acid and the like can be used. Since these amino acids are diamine monocarboxylic acids or monoamine dicarboxylic acids, the carboxyl group is esterified with an alkanolamine such as ethanolamine. Thereby, the obtained triamine having an ester group can be converted into a triisocyanate having an ester structure by phosgenation or the like.
Examples of the ether amine include “D403”, a product name of Mitsui Chemical Fine Inc., which is a polyoxyalkylene triamine. This is a triamine, and can be converted to a triisocyanate containing an ether structure by phosgenation of an amine or the like.
Examples of the alkyltriamine include triisocyanatononane (4-aminomethyl-1,8-octanediamine) and the like. This is a triamine, and can be converted into a triisocyanate containing only a hydrocarbon by phosgenation of the amine or the like.

As a method for producing an iminooxadiazinedione structure or an isocyanurate structure, there is a method using a catalyst. For example, the following catalysts (1) to (10) generally known as catalysts can be used.
(1) (poly) hydrogen fluoride represented by general formula M [Fn] or general formula M [Fn (HF) m] such as tetramethylammonium fluoride hydrate, tetraethylammonium fluoride, etc. In the formula, m and n are integers satisfying the relationship of m / n> 0, and M represents an n-charged cation (mixture) or one or more radicals having a total of n valence.)
(2) 3,3,3-trifluorocarboxylic acid; 4,4,4,3,3-pentafluorobutanoic acid; 5,5,5,4,4,3,3-heptafluoropentanoic acid; General formula R ¹ -C (2R ′) — C (O) O— such as 3-difluoroprop-2-enoic acid or general formula R ² ＝ CR′—C (O) O— (in the above general formula, R ¹ and R ² are, if necessary, a branched, cyclic, and / or unsaturated perfluoroalkyl group having 1 to 30 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, And a group containing an aryl group and optionally containing a hetero atom. A plurality of R's may be the same or different.) And a quaternary ammonium cation or a quaternary ammonium cation. A compound comprising a quaternary phosphonium cation.
(3) Tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium and tetrabutylammonium; organic acid salts thereof such as acetates, octylates, myristates and benzoates;
(4) Hydroxides of hydroxyalkylammonium such as trimethylhydroxyethylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium, and triethylhydroxypropylammonium; organic weak acids such as acetates, octylates, myristates, and benzoates; salt,
(5) metal salts such as tin, zinc and lead of alkyl carboxylic acids such as acetic acid, caproic acid, octylic acid and myristic acid;
(6) metal alcoholates such as sodium and potassium,
(7) an aminosilyl group-containing compound such as hexamethylene disilazane;
(8) Mannich bases,
(9) a combination of a tertiary amine and an epoxy compound,
(10) phosphorus compounds such as tributylphosphine,
And the like.
Among them, tetramethylammonium fluoride hydrate is preferable as the catalyst from the viewpoint of availability. From the viewpoint of safety, (2) is preferable. In addition, a quaternary ammonium organic weak acid salt is preferable from the viewpoint that unnecessary by-products are not easily generated.

These catalysts may be diluted with a solvent or added together with the solvent, from the viewpoint of catalyst mixing properties. As the solvent, for example, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, Propylene glycol monomethyl ether acetate, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, , 3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso- pentane, hexane, iso- hexane, cyclohexane, solvent naphtha, mineral spirits, dimethylformamide and the like. These catalysts may be used alone or in combination of two or more.
Among them, as the solvent, from the viewpoint of iminooxadiazinedione production, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol Ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, or 1,3-butanediol is preferred, and iso-butanol, 1-butanol, or 2-ethylhexanol is more preferred.

The reaction temperature for forming the iminooxadiazinedione structure or the isocyanurate structure is preferably from 40 ° C to 120 ° C. The lower limit of the temperature is preferably 50 ° C. or higher, more preferably 55 ° C. or higher. Further, the upper limit of the temperature is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 80 ° C. or lower. When the reaction temperature is equal to or higher than the lower limit, the reaction rate can be maintained. When the reaction temperature is equal to or lower than the upper limit, coloring of the polyisocyanate composition can be suppressed.
The reaction is not particularly limited, but is stopped by, for example, addition of an acidic compound such as phosphoric acid or an acidic phosphoric acid ester.

  The conversion of the polyisocyanate composition of Embodiment 1-1 is preferably 1% or more and 100% or less, more preferably 10% or more and 80% or less, and particularly preferably 20% or more and 70% or less. . Above the lower limit, the curability tends to be excellent, and below the upper limit, the viscosity tends to be low and the workability tends to be excellent.

  The conversion was determined by gel permeation chromatography (hereinafter referred to as "GPC"), and the area ratio of the peak having a number average molecular weight larger than that of the unreacted triisocyanate was determined by the number average molecular weight based on polystyrene.

The lower limit of the molar ratio of the iminooxadiazinedione structure to the isocyanurate structure of the polyisocyanate composition of the 1-1 embodiment is preferably 0.01 or more, and more preferably 0.02 or more. More preferably, it is more preferably 0.05 or more, and particularly preferably 0.1 or more. Further, the upper limit of the molar ratio is preferably 1.5 or less, more preferably 1.3 or less, further preferably 0.8 or less, and more preferably 0.4 or less. Particularly preferred. When the molar ratio is equal to or more than the lower limit, the adhesiveness with the underlying coating film tends to be better, and when the molar ratio is equal to or less than the upper limit, the drying property tends to be better. .

  The content of the polyisocyanate compound in the polyisocyanate composition of Embodiment 1-1 is not particularly limited, but is preferably 1% by mass or more and 100% by mass or less, and is preferably 10% by mass or more and 90% by mass or less. More preferably, it is 12% by mass or more and 80% by mass or less, further preferably 15% by mass or more and 77% by mass or less, further preferably 15% by mass or more and 75% by mass or less. , 20 mass% or more and 70 mass% or less. When it is at least the lower limit, weather resistance tends to be excellent, and when it is at most the upper limit, viscosity tends to be low and workability tends to be excellent.

In addition, the polyisocyanate composition of Embodiment 1-1 has a compound having an uretdione structure and an allophanate structure in addition to the polyisocyanate compound represented by the general formula (I) or the general formula (II). A compound, a compound having a urethane structure, or a compound having a buret structure may be included.
The uretdione structure, allophanate structure, urethane structure, or buret structure is represented by the following formula (VII), (VIII), (IX), or (X), respectively. Among them, a compound having an allophanate structure or a compound having a uretdione structure is preferable from the viewpoint of coating film hardness.

  It is preferable that the polyisocyanate composition of the first embodiment further includes a triisocyanate represented by the following general formula (V) -1. -General formula (V) -1

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

[R ⁵¹ , Y ¹ ]

Description of the general formula (V) ^R 51, ^{Y 1} in the -1 is the same as the description of ^R 51, ^{Y 1} in the general formula (V).
In the 1-1 embodiment, at least one of the plurality of Y ¹ preferably contains an ester structure and / or an ether structure.
In general formula (V) ^R 51, ^{Y 1} in the -1, ^R 51, ^{Y 1} and may be different may be the same in the general formula (V).

When made from known polyisocyanate compositions, e.g., volatile diisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentane diisocyanate, toluene diisocyanate or isophorone diisocyanate, the unreacted starting diisocyanate is finalized, for example, by distillation. It is necessary to remove from the product to less than 2% by weight, preferably less than 1% by weight, based on the weight of the polyisocyanate composition. However, when producing the polyisocyanate composition of the 1-1 embodiment, since the number of NCO groups of the triisocyanate used in the 1-1 embodiment is 3, the polyol of the polyisocyanate composition of the 1-1 embodiment is used. It does not necessarily reduce the cross-linking ability with the polymer and does not necessarily need to be removed.
When removing unreacted triisocyanate, it can be separated from the polyisocyanate composition by a thin-film distillation method, a solvent extraction method, or the like.

  The viscosity at 25 ° C. of the polyisocyanate composition of the 1-1 embodiment is not particularly limited, but is preferably 5 mPa · s or more and 1000 mPa · s or less, more preferably 8 mPa · s or more and 800 mPa · sm or less, It is more preferably from 10 mPa · s to 500 mPa · sm, particularly preferably from 10 mPa · s to 100 mPa · sm. Above the lower limit, curability tends to be excellent, and below the upper limit, workability tends to be excellent. The viscosity can be measured by using an E-type viscometer (manufactured by Tokimec).

The polyisocyanate composition of the 1-1 embodiment includes a polyisocyanate compound represented by the general formula (II), and has a theoretical reaction rate of 47% or less, calculated from NCO% of the polyisocyanate composition. Preferably, there is.
The theoretical reaction rate is more preferably 1% or more and 47% or less, further preferably 10% or more and 45% or less, and particularly preferably 15% or more and 45% or less. Above the lower limit, the curability tends to be excellent, and below the upper limit, the viscosity tends to be low, the workability is excellent, and the crack resistance of the coating film tends to be excellent.

The theoretical conversion is expressed as a conversion assuming that all multimers are trimers. The theoretical reaction rate c (%) is calculated based on the NCO% (x%) of the synthesized polyisocyanate composition, the NCO% (a%) of the used triisocyanate (see the following formula [B]), and the triisocyanate trimer. From NCO% (b%) (see the following formula [C]), it can be obtained by the following formula [D].
NCO% of triisocyanate used: (a) = (molecular weight of NCO / molecular weight of triisocyanate used) × 100 (%) [B]
NCO% of triisocyanate trimer: (b) = (molecular weight of NCO / molecular weight of triisocyanate trimer) × 100 (%) [C]
Theoretical reaction rate c (%) = [(xa) / (ba)] x 100 (%) [D]

The polyisocyanate composition of the 1-1 embodiment contains the polyisocyanate compound represented by the general formula (II), and has a theoretical conversion rate of 95 calculated from NCO% of the polyisocyanate composition. % Or more and 150% or less is preferable. The theoretical reaction rate is more preferably 100% or more and 130 or less, particularly preferably 100% or more and 120% or less. Above the lower limit, the hardness and water resistance of the coating film tend to be excellent, and below the upper limit, the amount of solvent used is small, and the solvent of the paint tends to be low.

In a 1-1 embodiment, the gel permeate includes a polyisocyanate compound (A) represented by the general formula (II) and a triisocyanate compound (B) represented by the general formula (V) -1. Of the peak area (A) of the number average molecular weight of the polyisocyanate compound (A) and the peak area (B) of the number average molecular weight of the triisocyanate compound (B), which are obtained by the application chromatography (GPC) measurement. The area ratio ((A) / [(A) + (B)]) is preferably 0.8 or more and less than 1.
The area ratio ((A) / [(A) + (B)]) by GPC measurement can be calculated by the method described in Examples.
The area ratio ((A) / [(A) + (B)]) of (A) and (B) by GPC measurement is preferably 0.85 or more and less than 1, and is 0.9 or more and less than 1. More preferably, there is.

When a monomer trimer in which all of R ^{21 in} the general formula (II) is a triisocyanate represented by the general formula (V) is a compound (C), measurement by gel permeation chromatography (GPC) is performed. The peak area (A) of the number average molecular weight of the polyisocyanate compound (A), the peak area (B) of the number average molecular weight of the triisocyanate compound (B), and the number average of the compound (C) obtained by The area ratio of the molecular weight to the peak area (C) ((C) / [(A) + (B)]) is from the viewpoint of optimizing all the drying properties, adhesion to the base material, and workability. It is preferably 3 or more and less than 1. The ratio is more preferably 0.35 or more and less than 1, and particularly preferably 0.4 or more and less than 1.

Further, the isocyanate group functionality is preferably 4 or more and 12 or less from the viewpoint of optimizing all of the drying property, the adhesion to the base substrate, and the workability. The functionality is more preferably 5 or more and 11 or less, and particularly preferably 6 or more and 9 or less.

[1-2nd Embodiment]

The polyisocyanate composition of the 1-2 embodiment of the present invention contains the polyisocyanate compounds represented by the general formulas (II) and (III), and the molar ratio of the isocyanurate structure to the allophanate structure is 100/0. 1 to 100/15.

［一般式（ＩＩ）および一般式（ＩＩＩ）中、複数あるＲ^２１およびＲ^３１は、それぞれ独立に、有機基であり、複数あるＲ^２１およびＲ^３１のうち少なくとも１つは一般式（Ｖ）で表される基である。複数あるＲ^２１およびＲ^３１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^３２は、１価以上のアルコールから１つのヒドロキシ基を除去した残基である。］

[In the general formulas (II) and (III), a plurality of R ²¹ and R ³¹ are each independently an organic group, and at least one of the plurality of R ²¹ and R ³¹ is a group represented by the general formula (V) Is a group represented by A plurality of R ²¹ and R ³¹ may be the same or different. R ³² is a residue obtained by removing one hydroxy group from a monovalent or higher alcohol. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］ 以下、一般式（ＩＩ）、一般式（ＩＩＩ）および一般式（Ｖ）について説明する。

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. Hereinafter, general formulas (II), (III) and (V) will be described.

-General formula (II)

一般式（ＩＩ）で表されるポリイソシアネート化合物は、イソシアヌレート構造を有する。イソシアヌレート構造は、トリイソシアネートモノマー３分子からなるポリイソシアネートである。

The polyisocyanate compound represented by the general formula (II) has an isocyanurate structure. The isocyanurate structure is a polyisocyanate composed of three triisocyanate monomer molecules.

[R ²¹ ]

In the general formula (II), a plurality of R ²¹ are each independently an organic group. A plurality of R ²¹ may be the same or different.
In the first 1-2 embodiment, of the three R ^21, at least one is a group represented by the general formula (V), groups in which two R ²¹ is represented by the general formula (V) It is more preferable that all three R ²¹ are groups represented by the above general formula (V).

Examples of the group other than the group represented by the general formula (V) in R ²¹ include, for example, tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,2,4 -Trimethylhexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate (MPDI), 1,3-bis (isocyanatomethyl) -cyclohexane (1,3-H6-XDI), 3 (4) -Isocyanatomethyl-1-methyl-cyclohexylisoanate (IMCI); isophorone diisocyanate (IPDI), bis (isocyanatomethyl) -norbornane (NBDI), 1,3-bis (isocyanatomethyl) -benzene, 1, 3-bis (2-isocyanatopropyl-2) benzene and And a residue obtained by removing one isocyanate group from 4,4′-dicyclohexylmethane diisocyanate (H12MDI).

・ General formula (III)

一般式（ＩＩＩ）で表されるポリイソシアネート化合物は、アロファネート構造を有する。アロファネート構造は、トリイソシアネートモノマー２分子と１価以上のアルコールからなるポリイソシアネートである。

The polyisocyanate compound represented by the general formula (III) has an allophanate structure. The allophanate structure is a polyisocyanate comprising two molecules of a triisocyanate monomer and a monohydric or higher alcohol.

[R ³¹ ]

In the general formula (III), a plurality of R ³¹ are each independently an organic group. A plurality of R ³¹ may be the same or different.
In the first 1-2 embodiment, of the three R ^31, at least one is a group represented by the general formula (V), groups in which two R ³¹ is represented by the general formula (V) It is more preferable that all three R ³¹ are groups represented by the above general formula (V).

Examples of the group other than the group represented by the general formula (V) in R ³¹ include, for example, the same groups as those exemplified in the above-described “• General formula (II)”.

[ ^R32 ]

In the general formula (III), R ³² is a residue obtained by removing one hydroxyl group from monovalent or polyvalent alcohols.
More specifically, R ³² is, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, 1-pentanol, 2-pentanol, isoamyl alcohol, -Saturated aliphatic alcohols such as hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol and pentadecanol, cyclohexanol, It is a residue obtained by removing one hydroxy group from a monohydric alcohol such as an unsaturated aliphatic alcohol such as a saturated cyclic aliphatic alcohol such as cyclopentanol, allyl alcohol, butenol, hexenol, or 2-hydroxyethyl acrylate.

  For example, ethylene glycol, propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,6-cyclohexanediol, 1,4-cyclohexanediol, A residue obtained by removing one hydroxy group from a dihydric alcohol such as methylpentanediol, cyclohexanedimethanol, methylpentanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, etc. .

  For example, one hydroxyl group is formed from a trihydric alcohol such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-hydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol. This is the residue from which the group has been removed.

  For example, it is a residue obtained by removing one hydroxy group from a tetrahydric alcohol such as sugar alcohol such as pentitol such as erythrose and pentitol such as xylitol and hexitol such as sorbitol.

  For example, it is a residue obtained by removing one hydroxy group from phenols such as phenol, benzylphenol, o-cresol, p-cresol, catechol, ethylphenol, octylphenol, xylenol, naphthol, nonylphenol and bisphenol A.

For example, a residue obtained by removing one hydroxy group from an alcohol such as polyester polyol, polypropylene glycol, polyethylene glycol, or polytetraethylene glycol using the above-mentioned alcohol as a raw material may be used.
For example, it may be a residue obtained by removing one hydroxy group from an acrylic polyol having a hydroxyl group.

Among these, as R ³² in the embodiment 1-2, the compatibility of the silicate from the viewpoint of film hardness is preferably monovalent removing residues one hydroxy group from an alcohol, carbon atoms is 3 to 9 A residue obtained by removing one hydroxy group from monovalent alcohol is more preferred, and a residue obtained by removing one hydroxy group from 1-butanol, iso-butanol, or 2-ethyl-1-hexanol is most preferred. When the carbon number is 3 or more, the compatibility with the silicate is good, and when the carbon number is 9 or less, sufficient scratch resistance can be imparted to the coating film.

The polyisocyanate composition of the first to second embodiments has an isocyanurate structure and an allophanate structure. The molar ratio between the isocyanurate structure and the allophanate structure is in the range of 100 / 0.1 to 100/15, preferably 100/1 to 100/12, more preferably 100/2 to 100/10, and more preferably 100/4. ~ 100/8 is more preferred. If it is less than the above upper limit, the abrasion resistance of the coating film is good, and if it is more than the above lower limit, the compatibility with the silicate is sufficient. The molar ratio between the isocyanurate structure and the allophanate structure in the polyisocyanate composition can be measured using, for example, ¹³ C-NMR.

・ General formula (V)

［Ｙ^１］

一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造［−Ｃ（＝Ｏ）−Ｏ−］および／またはエーテル構造（−Ｏ−）を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。
エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基としては、−（ＣＨ_２）_ｎ１−Ｘ−（ＣＨ_２）_ｎ２−で表される基（ｎ１およびｎ２はそれぞれ独立して、０〜１０の整数である。但し、ｎ１およびｎ２の両方とも０になることはなく、ｎ１、ｎ２のうち、ＮＣＯと結合している側は１以上であることが好ましい。Ｘは、エステル基またはエーテル基である）。
反応速度を速めたい場合、Ｘがエステル基であることが好ましい。
ｎ１及びｎ２は０〜４が好ましく、０〜２がより好ましい。ｎ１及びｎ２の組み合わせとしては、例えば、ｎ１＝０、ｎ２＝２の組み合わせ、ｎ１＝２、ｎ２＝２の組み合わせが好ましい。

[Y ¹ ]

In the general formula (V), a plurality of Y ¹ are each independently a single bond or a carbon which may contain an ester structure [—C (＝ O) —O—] and / or an ether structure (—O—). It is a divalent hydrocarbon group of the formulas 1 to 20. A plurality of Y ¹ may be the same or different.
Examples of the divalent hydrocarbon group having ester structure and / or carbon atoms which may contain an ether structure _{1~20, - (CH 2) n1} -X- (CH 2) n2 - group represented by (n1 and n2 Are each independently an integer from 0 to 10. However, both n1 and n2 do not become 0, and it is preferable that one of n1 and n2 bonded to NCO is 1 or more. X is an ester or ether group).
When it is desired to increase the reaction rate, X is preferably an ester group.
n1 and n2 are preferably from 0 to 4, more preferably from 0 to 2. As a combination of n1 and n2, for example, a combination of n1 = 0 and n2 = 2, and a combination of n1 = 2 and n2 = 2 are preferable.

[ ^R51 ]

R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group for R ⁵¹ is not particularly limited, and includes an alkyl group, an alkenyl group, an alkynyl group, and the like. As R ⁵¹ , a hydrogen atom is preferable.

It is preferable that the molecular weight of the triisocyanate which is the base of the group represented by the general formula (V) in the 1-2 embodiment is 139 or more and 1000 or less.
The lower limit of the molecular weight is preferably 150 or more, more preferably 180 or more, and particularly preferably 200 or more. The upper limit of the molecular weight is preferably 800 or less, more preferably 600 or less, and particularly preferably 400 or less. When the molecular weight is equal to or more than the above lower limit, crystallinity is easily suppressed. In addition, when the molecular weight is equal to or less than the above upper limit, lower viscosity can be easily achieved.

The triisocyanate that is the basis of the group represented by the general formula (V) in the first to second embodiments has a low viscosity, and therefore, a plurality of hydrocarbon groups in Y ¹ are an aliphatic group and / or an aromatic group. It is preferable to have Also, R ⁵¹ is preferably hydrogen.
Further, in order to improve the weather resistance when used as a curing agent of the coating composition, but preferably the hydrocarbon group in the plurality of Y ¹ is an aliphatic group or an alicyclic group.
In addition, it is preferable that a plurality of Y ¹ be composed of only a hydrocarbon group.
Separately, in order to maintain heat resistance, at least one of the plurality of Y ¹ preferably has an ester group.
In order to maintain hydrolysis resistance, at least one of the plurality of Y ³¹ preferably has a hydrocarbon group containing an ether structure or a hydrocarbon group.

Examples of the triisocyanate which is the basis of the group represented by the general formula (V) in the 1-2 embodiment include 4-isocyanatomethyl-1,8-octaphthalate disclosed in JP-B-63-15264. Methylene diisocyanate (hereinafter sometimes referred to as “NTI”, molecular weight 251), 1,3,6-hexamethylene triisocyanate (hereinafter referred to as “HTI”) disclosed in JP-A-57-198760. Bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter referred to as GTI, molecular weight 311) disclosed in JP-B-4-1033, JP-A-53-135931. Lysine triisocyanate (hereinafter, referred to as LTI, molecular weight 267) and the like.
Among these, NTI, GTI, or LTI is preferable, NTI or LTI is more preferable, and LTI is particularly preferable, from the viewpoint of further improving the reactivity of the isocyanate group.

The triisocyanate serving as the base of the group represented by the general formula (V) in the first to second embodiments can be obtained by isocyanating an amino acid derivative or an amine such as an etheramine or an alkyltriamine. As the amino acid derivative, for example, 2,5-diaminovaleric acid, 2,6-diaminohexanoic acid, aspartic acid, glutamic acid and the like can be used. Since these amino acids are diamine monocarboxylic acids or monoamine dicarboxylic acids, the carboxyl group is esterified with an alkanolamine such as ethanolamine. Thereby, the obtained triamine having an ester group can be converted into a triisocyanate having an ester structure by phosgenation or the like.
Examples of the ether amine include “D403”, a product name of Mitsui Chemical Fine Inc., which is a polyoxyalkylene triamine. This is a triamine, which can be converted to a triisocyanate containing an ether structure by phosgenation of an amine or the like.
Examples of the alkyltriamine include triisocyanatononane (4-aminomethyl-1,8-octanediamine) and the like. This is a triamine, and can be converted to a triisocyanate containing only a hydrocarbon by phosgenation of the amine or the like.

As a method for forming an isocyanurate structure and / or an allophanate structure, there is a method using an isocyanurate-forming catalyst. The isocyanurate-forming catalyst is not particularly limited, but generally has a basic property, for example,
(1) Tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium and tetrabutylammonium; organic weak salts such as acetates, octylates, myristates and benzoates;
(2) Hydroxides of hydroxyalkylammonium such as trimethylhydroxyethylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium, triethylhydroxypropylammonium; organic weak acids such as acetate, octylate, myristate, benzoate and the like. salt,
(3) metal salts such as tin, zinc and lead of alkyl carboxylic acids such as acetic acid, caproic acid, octylic acid and myristic acid;
(4) metal alcoholates such as sodium and potassium,
(5) an aminosilyl group-containing compound such as hexamethylene disilazane;
(6) Mannich bases,
(7) Combination of tertiary amines and epoxy compound,
(8) Phosphorus compounds such as tributylphosphine and the like.
Among them, a quaternary ammonium organic weak acid salt is preferable, and a tetraalkyl ammonium organic weak acid salt is more preferable, from the viewpoint of hardly generating unnecessary by-products.

  These catalysts may be diluted with a solvent or added together with the solvent, from the viewpoint of catalyst mixing properties. As the solvent, for example, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, Propylene glycol monomethyl ether acetate, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, , 3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit, dimethylformamide and the like. The above can be used in combination.

The isocyanuration reaction temperature is preferably from 50 ° C to 120 ° C, more preferably from 60 ° C to 90 ° C. When the content is not more than the above upper limit, coloring and the like tend to be effectively prevented, which is preferable.
The isocyanuration reaction is not particularly limited, but is stopped by, for example, addition of an acidic compound such as phosphoric acid or acidic phosphate.

  The conversion of the polyisocyanate composition of the 1-2 embodiment is preferably 1% or more and 100% or less, more preferably 10% or more and 80% or less, and particularly preferably 20% or more and 70% or less. . Above the lower limit, the curability tends to be excellent, and below the upper limit, the viscosity tends to be low and the workability tends to be excellent.

  The conversion was determined by gel permeation chromatography (hereinafter referred to as "GPC"), and the area ratio of the peak having a number average molecular weight larger than that of the unreacted triisocyanate was determined by the number average molecular weight based on polystyrene.

  The content of the polyisocyanate compound in the polyisocyanate composition of the 1-2 embodiment is preferably from 1% by mass to 100% by mass, more preferably from 10% by mass to 90% by mass, More preferably, it is 20% by mass or more and 80% by mass or less. When it is at least the lower limit, weather resistance tends to be excellent, and when it is at most the upper limit, viscosity tends to be low and workability tends to be excellent.

Further, in addition to the polyisocyanate compound represented by the general formula (I) or the general formula (II), a compound having a uretdione structure, an iminooxadiazine, A compound having a dione structure, a compound having a urethane structure, or a compound having a buret structure may be included.
The uretdione structure, iminooxadiazinedione structure, urethane structure, or buret structure is represented by the following formula (VII), (XI), (IX), or (X), respectively. Above all, a compound having a uretdione structure or a compound having an iminooxadiazinedione structure is preferred from the viewpoint of infiltration into the lower layer of the multilayer coating film.

It is preferable that the polyisocyanate composition of the 1-2 embodiment further contains a triisocyanate represented by the following general formula (V) -1. -General formula (V) -1

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

[R ⁵¹ , Y ¹ ]

Description of the general formula (V) ^R 51, ^{Y 1} in the -1 is the same as the description of ^R 51, ^{Y 1} in the general formula (V).
In the first to second embodiments, at least one of the plurality of Y ¹ preferably contains an ester structure and / or an ether structure.
In general formula (V) ^R 51, ^{Y 1} in the -1, ^R 51, ^{Y 1} and may be different may be the same in the general formula (V).

When made from known polyisocyanate compositions, e.g., volatile diisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentane diisocyanate, toluene diisocyanate or isophorone diisocyanate, the unreacted starting diisocyanate is finalized, for example, by distillation. It is necessary to remove from the product to less than 2% by weight, preferably less than 1% by weight, based on the weight of the polyisocyanate composition. However, when manufacturing the polyisocyanate composition of the 1-2 embodiment, the number of NCO groups of the triisocyanate used in the 1-2 embodiment is 3, and therefore the polyol of the polyisocyanate composition of the 1-2 embodiment is used. It does not necessarily reduce the cross-linking ability with the polymer and does not necessarily need to be removed.
When removing unreacted triisocyanate, it can be separated from the polyisocyanate composition by a thin-film distillation method, a solvent extraction method, or the like.

  The viscosity at 25 ° C. of the polyisocyanate composition of the 1-2 embodiment is not particularly limited, but is preferably 5 mPa · s or more and 2000 mPa · s or less, and is preferably 10 mPa · s or more and 1800 mPa · sm or less. More preferably, it is more preferably from 15 mPa · s to 250 mPa · s. Above the lower limit, curability tends to be excellent, and below the upper limit, workability tends to be excellent. The viscosity can be measured by using an E-type viscometer (manufactured by Tokimec).

[1-3 embodiment]
The polyisocyanate composition of the first to third embodiments of the present invention contains the polyisocyanate compounds represented by the general formulas (II) and (IV), and the molar ratio of the isocyanurate structure to the uretdione structure is 100/0. 1/100/100, preferably 100 / 0.1-100 / 45.
When the molar ratio is equal to or more than the lower limit, the adhesiveness with the underlying coating film tends to be better, and when the molar ratio is equal to or less than the upper limit, the drying property tends to be better. .

［一般式（ＩＩ）および（ＩＶ）中、複数あるＲ^２１およびＲ^４１は、それぞれ独立に、有機基であり、複数あるＲ^２１およびＲ^４１のうち少なくとも１つは一般式（Ｖ）で表される基である。複数あるＲ^２１およびＲ^４１は、それぞれ同一であってもよく異なっていてもよい。」

[In the general formulas (II) and (IV), a plurality of R ²¹ and R ⁴¹ are each independently an organic group, and at least one of the plurality of R ²¹ and R ⁴¹ is represented by the general formula (V). It is a group to be performed. A plurality of R ²¹ and R ⁴¹ may be the same or different. "

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］ 以下、一般式（ＩＩ）、一般式（ＩＶ）、および一般式（Ｖ）について説明する。
・一般式（ＩＩ）

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. Hereinafter, general formula (II), general formula (IV), and general formula (V) will be described.
-General formula (II)

一般式（ＩＩ）で表されるポリイソシアネート化合物は、イソシアヌレート構造を有する。イソシアヌレート構造は、トリイソシアネートモノマー３分子からなるポリイソシアネートである。

The polyisocyanate compound represented by the general formula (II) has an isocyanurate structure. The isocyanurate structure is a polyisocyanate composed of three triisocyanate monomer molecules.

[R ²¹ ]

In the general formula (II), a plurality of R ²¹ are each independently an organic group. A plurality of R ²¹ may be the same or different.
In the first 1-3 embodiment, of the three R ^21, at least one is a group represented by the general formula (V), groups in which two R ²¹ is represented by the general formula (V) It is more preferable that all three R ²¹ are groups represented by the above general formula (V).

Examples of the group other than the group represented by the general formula (V) in R ²¹ include, for example, tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,2,4 -Trimethylhexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate (MPDI), 1,3-bis (isocyanatomethyl) -cyclohexane (1,3-H6-XDI), 3 (4) -Isocyanatomethyl-1-methyl-cyclohexylisoanate (IMCI); isophorone diisocyanate (IPDI), bis (isocyanatomethyl) -norbornane (NBDI), 1,3-bis (isocyanatomethyl) -benzene, 1, 3-bis (2-isocyanatopropyl-2) benzene and And a residue obtained by removing one isocyanate group from 4,4′-dicyclohexylmethane diisocyanate (H12MDI). -General formula (IV)

一般式（ＩＶ）において、複数あるＲ^４１は、前記「・一般式（ＩＩ）におけるＲ^２１と同様である。・一般式（Ｖ）

In the general formula (IV), a plurality of R ⁴¹ are the same as those of “R ²¹ in the general formula (II).

［Ｙ^１］

一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造［−Ｃ（＝Ｏ）−Ｏ−］および／またはエーテル構造（−Ｏ−）を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。
エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基としては、−（ＣＨ_２）_ｎ１−Ｘ−（ＣＨ_２）_ｎ２−で表される基（ｎ１およびｎ２はそれぞれ独立して、０〜１０の整数である。但し、ｎ１およびｎ２の両方とも０になることはなく、ｎ１、ｎ２のうち、ＮＣＯと結合している側は１以上であることが好ましい。Ｘは、エステル基またはエーテル基である）。
反応速度を速めたい場合、Ｘがエステル基であることが好ましい。
ｎ１及びｎ２は０〜４が好ましく、０〜２がより好ましい。ｎ１及びｎ２の組み合わせとしては、例えば、ｎ１＝０、ｎ２＝２の組み合わせ、ｎ１＝２、ｎ２＝２の組み合わせが好ましい。

[Y ¹ ]

In the general formula (V), a plurality of Y ¹ are each independently a single bond or a carbon which may contain an ester structure [—C (＝ O) —O—] and / or an ether structure (—O—). It is a divalent hydrocarbon group of the formulas 1 to 20. A plurality of Y ¹ may be the same or different.
Examples of the divalent hydrocarbon group having ester structure and / or carbon atoms which may contain an ether structure _{1~20, - (CH 2) n1} -X- (CH 2) n2 - group represented by (n1 and n2 Are each independently an integer from 0 to 10. However, both n1 and n2 do not become 0, and it is preferable that one of n1 and n2 bonded to NCO is 1 or more. X is an ester or ether group).
When it is desired to increase the reaction rate, X is preferably an ester group.
n1 and n2 are preferably from 0 to 4, more preferably from 0 to 2. As a combination of n1 and n2, for example, a combination of n1 = 0 and n2 = 2, and a combination of n1 = 2 and n2 = 2 are preferable.

[ ^R51 ]

R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group for R ⁵¹ is not particularly limited, and includes an alkyl group, an alkenyl group, an alkynyl group, and the like. As R ⁵¹ , a hydrogen atom is preferable.

It is preferable that the molecular weight of the triisocyanate that is the base of the group represented by the general formula (V) in the first to third embodiments is 139 or more and 1000 or less.
The lower limit of the molecular weight is preferably 150 or more, more preferably 180 or more, and particularly preferably 200 or more. The upper limit of the molecular weight is preferably 800 or less, more preferably 600 or less, and particularly preferably 400 or less. When the molecular weight is equal to or more than the above lower limit, crystallinity is easily suppressed. In addition, when the molecular weight is equal to or less than the above upper limit, lower viscosity can be easily achieved.

The triisocyanate which is the base of the group represented by the general formula (V) in the first to third embodiments has a low viscosity, and therefore, a plurality of hydrocarbon groups in Y ¹ are an aliphatic group and / or an aromatic group. It is preferable to have Also, R ⁵¹ is preferably hydrogen.
Further, in order to improve the weather resistance when used as a curing agent of the coating composition, but preferably the hydrocarbon group in the plurality of Y ¹ is an aliphatic group or an alicyclic group.
In addition, it is preferable that a plurality of Y ¹ be composed of only a hydrocarbon group.
Separately, in order to maintain heat resistance, at least one of the plurality of Y ¹ preferably has an ester group.
In order to maintain hydrolysis resistance, at least one of the plurality of Y ³¹ preferably has a hydrocarbon group containing an ether structure or a hydrocarbon group.

Examples of the triisocyanate which is a source of the group represented by the general formula (V) in the first to third embodiments include 4-isocyanatomethyl-1,8-octaphthalate disclosed in JP-B-63-15264. Methylene diisocyanate (hereinafter sometimes referred to as “NTI”, molecular weight 251), 1,3,6-hexamethylene triisocyanate (hereinafter referred to as “HTI”) disclosed in JP-A-57-198760. Bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter referred to as GTI, molecular weight 311) disclosed in JP-B-4-1033, JP-A-53-135931. Lysine triisocyanate (hereinafter, referred to as LTI, molecular weight 267) and the like.
Among these, NTI, GTI, or LTI is preferable, NTI or LTI is more preferable, and LTI is particularly preferable, from the viewpoint of further improving the reactivity of the isocyanate group.

The triisocyanate which is the base of the group represented by the general formula (V) in the first to third embodiments can be obtained by isocyanating an amino acid derivative or an amine such as an etheramine or an alkyltriamine. As the amino acid derivative, for example, 2,5-diaminovaleric acid, 2,6-diaminohexanoic acid, aspartic acid, glutamic acid and the like can be used. Since these amino acids are diamine monocarboxylic acids or monoamine dicarboxylic acids, the carboxyl group is esterified with an alkanolamine such as ethanolamine. Thereby, the obtained triamine having an ester group can be converted into a triisocyanate having an ester structure by phosgenation or the like.
Examples of the ether amine include “D403”, a product name of Mitsui Chemical Fine Inc., which is a polyoxyalkylene triamine. This is a triamine, which can be converted to a triisocyanate containing an ether structure by phosgenation of an amine or the like.
Examples of the alkyltriamine include triisocyanatononane (4-aminomethyl-1,8-octanediamine) and the like. This is a triamine, and can be converted to a triisocyanate containing only a hydrocarbon by phosgenation of the amine or the like.

As a method for forming an isocyanurate structure and / or an allophanate structure, there is a method using an isocyanurate-forming catalyst. The isocyanurate-forming catalyst is not particularly limited, but generally has a basic property, for example,
(1) Tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium and tetrabutylammonium; organic weak salts such as acetates, octylates, myristates and benzoates;
(2) Hydroxides of hydroxyalkylammonium such as trimethylhydroxyethylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium, triethylhydroxypropylammonium; organic weak acids such as acetate, octylate, myristate, benzoate and the like. salt,
(3) metal salts such as tin, zinc and lead of alkyl carboxylic acids such as acetic acid, caproic acid, octylic acid and myristic acid;
(4) metal alcoholates such as sodium and potassium,
(5) an aminosilyl group-containing compound such as hexamethylene disilazane;
(6) Mannich bases,
(7) Combination of tertiary amines and epoxy compound,
(8) Phosphorus compounds such as tributylphosphine and the like.
Among them, a quaternary ammonium organic weak acid salt is preferable, and a tetraalkyl ammonium organic weak acid salt is more preferable, from the viewpoint of hardly generating unnecessary by-products.

  These catalysts may be diluted with a solvent or added together with the solvent, from the viewpoint of catalyst mixing properties. As the solvent, for example, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, Propylene glycol monomethyl ether acetate, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, , 3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit, dimethylformamide and the like. The above can be used in combination.

The isocyanuration reaction temperature is preferably from 50 ° C to 120 ° C, more preferably from 60 ° C to 90 ° C. When the content is not more than the above upper limit, coloring and the like tend to be effectively prevented, which is preferable.
The isocyanuration reaction is not particularly limited, but is stopped by, for example, addition of an acidic compound such as phosphoric acid or acidic phosphate.

As a method of forming the uretdione structure, there are a method using a uretdionation catalyst and a method of forming the uretdione structure by a high-temperature treatment at 100 ° C. or higher without using a uretdionation catalyst. First, the uretdionation catalyst is not particularly limited, but generally known uretdionation catalysts such as triethylphosphine, dibutylethylphosphine, tri-n-propylphosphine, triamylphosphine, trialkylphosphines such as tribenzylmethylphosphine, or In the presence of pyridine or the like, at a reaction temperature of 0 to 90 ° C., in the absence of a solvent, or in an inert solvent such as toluene, xylene or another aromatic solvent, methyl ethyl ketone, a ketone solvent such as methyl isobutyl ketone, ethyl acetate, It can be produced in the presence of an ester solvent such as butyl acetate and a glycol ether ester solvent such as propylene glycol methyl ether acetate and ethyl-3-ethoxypropionate.

  These catalysts may be diluted with a solvent or added together with the solvent, from the viewpoint of catalyst mixing properties. As the solvent, for example, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, Propylene glycol monomethyl ether acetate, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, , 3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit, dimethylformamide and the like. The above can be used in combination.

In the present invention, a promoter can be optionally used in addition to the above-mentioned catalyst. The co-catalyst is preferably an organic compound having at least one hydrogen atom bonded to oxygen, nitrogen or sulfur and having a pKa of at least 6. Suitable cocatalysts are low molecular weight monohydric or polyhydric alcohols having a molecular weight of 32 to 200, or mixtures of said alcohols. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2-ethyl-1-hexanol, 1-methoxy-2-propanol, ethylene glycol, propylene glycol, isomeric butanediol, hexanediol and Octanediol, diethylene glycol, dipropylene glycol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethylpentanediol, glycerol, trimethylolpropane and mixtures of these and / or other alcohols.

The reaction temperature at the time of uretdionation using a uretdionation catalyst is preferably from 0 ° C to 100 ° C, more preferably from 25 ° C to 90 ° C. When the content is not more than the above upper limit, coloring and the like tend to be effectively prevented, which is preferable. The termination of the uretdionation reaction is not particularly limited, but upon reaching a desired reaction rate, for example, a solution of phosphoric acid, methyl paratoluenesulfonate, sulfur or the like is added to inactivate the uretdionation catalyst and stop the reaction. .

A uretdione structure can be formed by high-temperature treatment without using a uretdione-forming catalyst. The processing temperature at the time of forming the uretdione structure is preferably from 100 ° C to 200 ° C, more preferably from 120 ° C to 180 ° C, and even more preferably from 150 ° C to 170 ° C. When the amount is equal to or less than the above upper limit, coloring or the like tends to be effectively prevented, and when the amount is equal to or more than the lower limit, there is a tendency to form efficiently, which is preferable.
When producing a uretdione structure by this method, after synthesizing another structure, a heat treatment may be performed in the presence of a triisocyanate monomer, or first, a heat treatment may be performed only with the triisocyanate monomer to perform uretdione structure. A structure may be synthesized and then another structure may be synthesized. By doing so, the uretdione-containing polyisocyanate composition can be synthesized at a time.

  The conversion of the polyisocyanate composition of the first to third embodiments is preferably 1% or more and 100% or less, more preferably 10% or more and 80% or less, and particularly preferably 20% or more and 70% or less. . Above the lower limit, the curability tends to be excellent, and below the upper limit, the viscosity tends to be low and the workability tends to be excellent.

  The conversion was determined by gel permeation chromatography (hereinafter referred to as "GPC"), and the area ratio of the peak having a number average molecular weight larger than that of the unreacted triisocyanate was determined by the number average molecular weight based on polystyrene.

  The content of the polyisocyanate compound in the polyisocyanate composition of the first to third embodiments is preferably from 1% by mass to 100% by mass, more preferably from 10% by mass to 90% by mass, More preferably, it is 20% by mass or more and 80% by mass or less. When it is at least the lower limit, weather resistance tends to be excellent, and when it is at most the upper limit, viscosity tends to be low and workability tends to be excellent.

The polyisocyanate composition according to the first to third embodiments includes, in addition to the polyisocyanate compound represented by the general formula (I) or the general formula (II), a compound having an allophanate structure, iminooxadiazine A compound having a dione structure, a compound having a urethane structure, or a compound having a buret structure may be included.
The allophanate structure, iminooxadiazinedione structure, urethane structure, or burette structure is represented by the following formula (VIII), (XI), (IX), or (X), respectively. Among them, a compound having an iminooxadiazinedione structure is preferable from the viewpoint of infiltration into the lower layer of the multilayer coating film, and a compound having an allophanate structure is preferable from the viewpoint of compatibility with silicate.

The polyisocyanate composition of the first to third embodiments preferably further contains a triisocyanate represented by the following general formula (V) -1. -General formula (V) -1

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

[R ⁵¹ , Y ¹ ]
Description of the general formula (V) ^R 51, ^{Y 1} in the -1 is the same as the description of ^R 51, ^{Y 1} in the general formula (V).
In the first to third embodiments, at least one of the plurality of Y ¹ preferably contains an ester structure and / or an ether structure.
In general formula (V) ^R 51, ^{Y 1} in the -1, ^R 51, ^{Y 1} and may be different may be the same in the general formula (V).

When made from known polyisocyanate compositions, e.g., volatile diisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentane diisocyanate, toluene diisocyanate or isophorone diisocyanate, the unreacted starting diisocyanate is finalized, for example, by distillation. It is necessary to remove from the product to less than 2% by weight, preferably less than 1% by weight, based on the weight of the polyisocyanate composition. However, when producing the polyisocyanate composition of the first to third embodiments, the polyol of the polyisocyanate composition of the first to third embodiments has three NCO groups in the triisocyanate used in the first to third embodiments. It does not necessarily reduce the cross-linking ability with the polymer and does not necessarily need to be removed.
When removing unreacted triisocyanate, it can be separated from the polyisocyanate composition by a thin-film distillation method, a solvent extraction method, or the like.

  The viscosity at 25 ° C. of the polyisocyanate composition of the first to third embodiments is not particularly limited, but is preferably 5 mPa · s or more and 3000 mPa · s or less, and is preferably 10 mPa · s or more and 1800 mPa · sm or less. More preferably, it is more preferably from 15 mPa · s to 250 mPa · s. Above the lower limit, curability tends to be excellent, and below the upper limit, workability tends to be excellent. The viscosity can be measured by using an E-type viscometer (manufactured by Tokimec).

[First to fourth embodiments]

The polyisocyanate composition of the first to fourth embodiments of the present invention contains a polyisocyanate compound represented by the general formula (II).

［一般式（ＩＩ）中、Ｒ^２１は有機基である。複数あるＲ^２１のうち少なくとも１つは、一般式（Ｖ）で表される基、または一般式（ＶＩ）で表される基である。複数あるＲ^２１は、それぞれ同一であってもよく異なっていてもよい。］

[In the general formula (II), R ²¹ is an organic group. At least one of the plurality of R ²¹ is a group represented by the general formula (V) or a group represented by the general formula (VI). A plurality of R ²¹ may be the same or different. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

［一般式（ＶＩ）中、Ｙ^２はエステル構造を含む炭素数１〜２０の２価の炭化水素基である。波線は結合手を意味する。］
以下、一般式（ＩＩ）、一般式（Ｖ）、一般式（ＩＶ）、および一般式（ＶＩ）について説明する。・一般式（ＩＩ）

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond. ]
Hereinafter, the general formula (II), the general formula (V), the general formula (IV), and the general formula (VI) will be described. -General formula (II)

  The polyisocyanate compound represented by the general formula (II) has an isocyanurate structure. The isocyanurate structure is a polyisocyanate composed of three molecules of an isocyanate monomer.

[R ²¹ ]

In the general formula (II), R ²¹ is an organic group. At least one of the plurality of R ²¹ is a group represented by the following general formula (V) or a group represented by the following general formula (VI). A plurality of R ²¹ may be the same or different.
In the first to fourth embodiments, at least one of the three R ²¹ is a group represented by the following general formula (V) or a group represented by the following general formula (VI); R ²¹ is preferably a group represented by the following general formula (V) or a group represented by the following general formula (VI), and all three R ²¹ are groups represented by the following general formula (V) Or a group represented by the following general formula (VI).

Examples of the group other than the group represented by the general formula (V) or the group other than the group represented by the general formula (VI) in R ²¹ include, for example, tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate (MPDI), 1,3-bis (isocyanatomethyl) -Cyclohexane (1,3-H6-XDI), 3 (4) -isocyanatomethyl-1-methyl-cyclohexylisoanate (IMCI); isophorone diisocyanate (IPDI), bis (isocyanatomethyl) -norbornane (NBDI) , 1,3-bis (isocyanatomethyl) -benzene, 1,3-bi And a residue obtained by removing an isocyanate group from di (2-isocyanatopropyl-2) benzene and 4,4′-dicyclohexylmethane diisocyanate (H12MDI).

・ General formula (V)

〔Ｙ^１〕

一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造［−Ｃ（＝Ｏ）−Ｏ−］及び／又はエーテル構造（−Ｏ−）を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数存在するＹ^１は、それぞれ同一であってもよく異なっていてもよい。但し、複数あるＹ^１のうち少なくとも１つは、エステル構造を含む。
エステル構造及び／又はエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基としては、−（ＣＨ_２）_ｎ１−Ｘ−（ＣＨ_２）_ｎ２−で表される基（ｎ１及びｎ２はそれぞれ独立して、０〜１０の整数である。但し、ｎ１及びｎ２の両方とも０になることはなく、ｎ１、ｎ２のうち、ＮＣＯと結合している側は１以上であることが好ましい。Ｘは、エステル基またはエーテル基である）。
反応速度を速めたい場合、Ｘがエステル基であることが好ましい。
ｎ１及びｎ２は０〜４が好ましく、０〜２がより好ましい。ｎ１及びｎ２の組み合わせとしては、例えば、ｎ１＝０、ｎ２＝２の組み合わせ、ｎ１＝２、ｎ２＝２の組み合わせが好ましい。

[Y ¹ ]

In the general formula (V), a plurality of Y ¹ are each independently a single bond or a carbon which may contain an ester structure [—C (＝ O) —O—] and / or an ether structure (—O—). It is a divalent hydrocarbon group of the formulas 1 to 20. A plurality of Y ¹ may be the same or different. However, at least ^one of the plurality of Y ¹ includes an ester structure.
Examples of the divalent hydrocarbon group having ester structure and / or carbon atoms which may contain an ether structure _{1~20, - (CH 2) n1} -X- (CH 2) n2 - group represented by (n1 and n2 Are each independently an integer from 0 to 10. However, both n1 and n2 do not become 0, and the side of n1 and n2 that is bonded to NCO is preferably 1 or more. X is an ester or ether group).
When it is desired to increase the reaction rate, X is preferably an ester group.
n1 and n2 are preferably from 0 to 4, more preferably from 0 to 2. As a combination of n1 and n2, for example, a combination of n1 = 0 and n2 = 2, and a combination of n1 = 2 and n2 = 2 are preferable.

[R ⁵¹ ]

R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group for R ⁵¹ is not particularly limited, and includes an alkyl group, an alkenyl group, an alkynyl group, and the like. As R ⁵¹ , a hydrogen atom is preferable.

It is preferable that the molecular weight of the triisocyanate that is the base of the group represented by the general formula (V) in the first to fourth embodiments is 139 or more and 1000 or less.
The lower limit of the molecular weight is preferably 150 or more, more preferably 180 or more, and particularly preferably 200 or more. The upper limit of the molecular weight is preferably 800 or less, more preferably 600 or less, and particularly preferably 400 or less. When the molecular weight is equal to or more than the above lower limit, crystallinity is easily suppressed. In addition, when the molecular weight is equal to or less than the above upper limit, lower viscosity can be easily achieved.

Since the triisocyanate that is the base of the group represented by the general formula (V) in the first to fourth embodiments has a low viscosity, a plurality of hydrocarbon groups in Y ¹ are an aliphatic group and / or an aromatic group. It preferably has a group. Also, R ⁵¹ is preferably hydrogen.
Further, in order to improve the weather resistance when used as a curing agent of the coating composition, a hydrocarbon group in Y ¹ preferably has an aliphatic group or an alicyclic group.
Separately, in order to maintain heat resistance, at least one of a plurality of Y ¹ preferably has an ester group.

Examples of the triisocyanate that is a source of the group represented by the general formula (V) in the first to fourth embodiments include bis (2-isocyanatoethyl) 2- disclosed in Japanese Patent Publication No. Hei 4-1033. Examples include isocyanatoglutarate (hereinafter, referred to as GTI, molecular weight 311) and lysine triisocyanate (hereinafter, referred to as LTI, molecular weight 267) disclosed in JP-A-53-135931.
Among these, LTI is particularly preferred from the viewpoint of further improving the reactivity of the isocyanate group.

Further, in order to maintain hydrolysis resistance, at least one of the plurality of Y ¹ preferably has a hydrocarbon group containing an ether structure. -General formula (VI)

〔Ｙ^２〕
一般式（ＶＩ）中、Ｙ^２はエステル構造を含む炭素数１〜２０の２価の炭化水素基である。

[Y ² ]
In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and containing an ester structure.

The diisocyanate serving as the base of the group represented by the general formula (VI) in the first to fourth embodiments has an ester structure in order to increase the reactivity of the isocyanate group when used as a curing agent of the coating composition.
Further, the hydrocarbon group in Y ² preferably has an aliphatic group or an aromatic group in the structure in order to have a low viscosity. In order to maintain heat resistance, Y ² is a hydrocarbon group having an ester structure. It is preferable to have
Examples of this category include lysine diisocyanate (hereinafter, LDI).

  The triisocyanate as the base of the group represented by the general formula (V) or the diisocyanate as the base of the group represented by the general formula (VI) in the first to fourth embodiments is obtained by converting an amine such as an amino acid derivative into isocyanate. Obtainable. As the amino acid derivative, for example, 2,5-diaminovaleric acid, 2,6-diaminohexanoic acid, aspartic acid, glutamic acid and the like can be used. Since these amino acids are diamine monocarboxylic acid or monoamine dicarboxylic acid, the number of amino groups is controlled by esterifying the carboxyl group with an alkanolamine such as ethanolamine, or esterifying the carboxyl group with methanol or the like. can do. The resulting amine having an ester group can be converted to a triisocyanate or diisocyanate containing an ester structure by phosgenation or the like.

As a method for forming the isocyanurate structure, there is a method using a catalyst. The isocyanuration catalyst is not particularly limited, but is preferably a basic one. For example, (1) tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium and tetrabutylammonium; acetates thereof, octyl Organic weak acid salts such as acid salts, myristic acid salts and benzoic acid salts; (2) hydroxyalkyl ammonium hydroxides such as trimethylhydroxyethylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium and triethylhydroxypropylammonium; acetates thereof Organic weak acid salts such as octylate, myristate and benzoate, (3) tin alkyl carboxylate such as acetic acid, caproic acid, octylic acid and myristic acid; Lead, metal salts such as lead, (4) metal alcoholates such as sodium and potassium, (5) aminosilyl group-containing compounds such as hexamethylene disilazane, (6) Mannich bases, (7) tertiary amines and epoxy And (8) phosphorus compounds such as tributylphosphine.
Among them, a quaternary ammonium organic weak acid salt is preferable, and a tetraalkyl ammonium organic weak acid salt is more preferable, from the viewpoint of hardly generating unnecessary by-products.

  These catalysts may be diluted with a solvent or added together with the solvent, from the viewpoint of the mixing property of the catalyst. As the solvent, for example, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, Propylene glycol monomethyl ether acetate, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, , 3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit, dimethylformamide and the like. The above can be used in combination.

The isocyanuration reaction temperature is preferably from 50 ° C to 120 ° C, more preferably from 60 ° C to 90 ° C. When the content is not more than the above upper limit, coloring and the like tend to be effectively prevented, which is preferable.
The isocyanuration reaction is not particularly limited, but is stopped by, for example, addition of an acidic compound such as phosphoric acid or acidic phosphate.
The conversion of the polyisocyanate composition of the first to fourth embodiments is preferably 1% or more and 100% or less, more preferably 10% or more and 80% or less, and particularly preferably 20% or more and 70% or less. Above the lower limit, the curability tends to be excellent, and below the upper limit, the viscosity tends to be low and the workability tends to be excellent.

  The conversion was determined by gel permeation chromatography (hereinafter referred to as "GPC"), and the area ratio of the peak having a number average molecular weight larger than that of the unreacted triisocyanate was determined by the number average molecular weight based on polystyrene.

  The content of the polyisocyanate compound in the polyisocyanate composition of the first to fourth embodiments is preferably from 1% by mass to 100% by mass, more preferably from 10% by mass to 90% by mass, More preferably, it is 20% by mass or more and 80% by mass or less. When it is at least the lower limit, weather resistance tends to be excellent, and when it is at most the upper limit, viscosity tends to be low and workability tends to be excellent.

In addition, in addition to the polyisocyanate compound represented by the general formula (II), the polyisocyanate composition of the first to fourth embodiments includes a compound having an uretdione structure, a compound having an allophanate structure, and an iminooxadiazinedione structure. , A compound having a urethane structure, and a compound having a buret structure.
The uretdione structure, allophanate structure, iminooxadiazinedione structure, urethane structure, and burette structure are represented by the following formulas (VII), (VIII), (XI), (IX), and (X), respectively. Among them, a compound having an allophanate structure, a compound having a uretdione structure, and a compound having an iminooxadiazinedione iminooxadiazinedione structure are preferred from the viewpoint of the ability to penetrate into the lower layer of the multilayer coating film.

The polyisocyanate composition according to the first to fourth embodiments has a reaction rate ( ^Vh ) between the polyisocyanate composition and the primary alcohol, which is higher than the reaction rate (Vh) between the polyisocyanate derived from hexamethylene diisocyanate and the primary alcohol. the ratio of ^{p) (V h / V p} ) is preferably less than 5 or 13.

Ratio of the reaction rate ( ^Vp ) of the polyisocyanate derived from hexamethylene diisocyanate and the primary alcohol to the reaction rate ( ^Vh ) of the polyisocyanate composition of the first to fourth embodiments with the primary alcohol ( ^Vp ) ( ^Vh / ^Vp ) is preferably greater than 1 and more preferably 5 or more from the viewpoint of drying property of the coating film. Further, from the viewpoint of the pot life of the coating material, it is preferably less than 15, more preferably less than 13.
The upper limit and the lower limit can be arbitrarily combined, but are preferably 5 or more and less than 13 in the first to fourth embodiments.

The reaction rate between the polyisocyanate composition and the primary alcohol can be measured, for example, by the following method.
The polyisocyanate composition is mixed so that the molar ratio of the NCO group to the OH group of the primary alcohol becomes 1, heated and stirred at 70 ° C., the residual rate of the NCO group is measured, and the rate of decrease is defined as the reaction rate. The residual ratio of NCO groups can be determined, for example, by measuring the NCO content.

  Examples of the primary alcohol include 1-butanol, iso-butanol, 2-ethylhexanol and the like. Examples of the polyisocyanate derived from the above hexamethylene diisocyanate include “Duranate TKA-100” and “Duranate TPA-100” (trade names) of Asahi Kasei Corporation.

  The polyisocyanate composition according to the first to fourth embodiments can be prepared, for example, by the following methods: 1) a method of producing the above-mentioned triisocyanate by isocyanuration, and 2) 0.4 to 0.6 mol of NCO of the above-mentioned triisocyanate. There is a method in which a group is produced by reacting a group with a thermal dissociating agent, performing isocyanuration, and then dissociating the thermal dissociating agent by heating or the like. Examples of the thermal dissociating agent include methyl ethyl ketoxime. In the production method (2), a polyisocyanate composition having a high reaction rate between the polyisocyanate composition and the primary alcohol can be obtained, which is preferable from the viewpoint of quick drying of the coating.

The polyisocyanate composition of the first to fourth embodiments preferably further contains a triisocyanate represented by the following general formula (V) -1 or a diisocyanate represented by the following general formula (VI) -1. -General formula (V) -1

［一般式（Ｖ）−１中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造及び／又はエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子又は炭素数１〜１２の１価の炭化水素基である。］

[In the general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

[R ⁵¹ , Y ¹ ]

The description regarding R ⁵¹ and Y ¹ in the general formula (V) -1 is the same as the description regarding R ¹ and Y ¹ in the general formula (V).
However, in the general formula (V) -1, Y ¹ may or may not contain an ester structure and / or an ether structure. In the first to fourth embodiments, at least one of the plurality of Y ¹ preferably contains an ester structure and / or an ether structure. -General formula (VI) -1

［一般式（ＶＩ）−１中、Ｙ^２はエステル構造を含んでいてもよい炭素数１〜２０の２価の炭化水素基である。］〔Ｙ^２〕

一般式（ＶＩ）−１中のＹ^２に関する説明は、前記一般式（ＶＩ）中のＹ^２に関する説明と同様である。
ただし、一般式（ＶＩ）−１においては、Ｙ^２はエステル構造及び／又はエーテル構造を含んでもよく、含んでいなくてもよい。第１−４実施形態においては、Ｙ^２はエステル構造及び／又はエーテル構造を含むことが好ましい。

[In general formula (VI) -1, Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ester structure. ] [Y ² ]

Description of the general formula (VI) in -1 ^{Y 2} are the same as the description of ^{Y 2} in the general formula (VI).
However, in the general formula (VI) -1, Y ² may or may not contain an ester structure and / or an ether structure. In the first to fourth embodiments, Y ² preferably contains an ester structure and / or an ether structure.

When the known polyisocyanate compositions are prepared from volatile diisocyanates such as, for example, 1,6-hexamethylene diisocyanate, 1,5-pentane diisocyanate, toluene diisocyanate or isophorone diisocyanate, the unreacted starting diisocyanate is finally formed, for example by distillation. It is necessary to remove from the product to less than 2% by weight, preferably less than 1% by weight based on the weight of the polyisocyanate composition. However, when producing the polyisocyanate composition of the first to fourth embodiments, since the number of NCO groups of the triisocyanate used in the first to fourth embodiments is 3, the polyol of the polyisocyanate composition of the first to fourth embodiments is used. It does not necessarily reduce the cross-linking ability with the polymer and does not necessarily need to be removed.
When removing unreacted triisocyanate, it can be separated from the polyisocyanate composition by a thin-film distillation method, a solvent extraction method, or the like.

  The viscosity at 25 ° C of the polyisocyanate composition of the first to fourth embodiments is not particularly limited, but is preferably 5 mPa · s to 2000 mPa · s, and more preferably 10 mPa · s to 1800 mPa · sm. Above the lower limit, curability tends to be excellent, and below the upper limit, workability tends to be excellent. The viscosity can be measured by using an E-type viscometer (manufactured by Tokimec).

[1-5th Embodiment]

The polyisocyanate composition of the first to fifth embodiments contains a polyisocyanate compound having an allophanate structure represented by the general formula (III), and isocyanate groups, allophanate structure, isocyanurate structure, uretdione contained in the polyisocyanate composition. Structure element, iminooxadiazinedione structure, urethane structure, and nitrogen element contained in the allophanate structure with respect to the total number of nitrogen elements contained in the burette structure (excluding the nitrogen element contained in R ³¹ and R ³² ) Is 1.5% or more and 60% or less.

［一般式（ＩＩＩ）中、Ｒ^３２は有機基である。複数あるＲ^３２のうち少なくとも１つは、一般式（Ｖ）で示される基であり、Ｒ^３２は１価以上のアルコールのヒドロキシル基を除去した残基である。］

[In the general formula (III), R ³² is an organic group. At least one of the plurality of R ³² is a group represented by the general formula (V), and R ³² is a residue obtained by removing a hydroxyl group of a monohydric or higher alcohol. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］ 以下、一般式（ＩＩＩ）および一般式（Ｖ）について説明する。

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. Hereinafter, the general formulas (III) and (V) will be described.

・ General formula (III)

一般式（ＩＩＩ）で表される化合物は、イソシアネート２分子と、１価以上のアルコールからなるアロファネート構造を有するポリイソシアネート化合物である。

The compound represented by the general formula (III) is a polyisocyanate compound having an allophanate structure composed of two molecules of isocyanate and a monohydric or higher alcohol.

[R ³¹ ]

In the general formula (III), at least one of R ³¹ is a group represented by the general formula (V).

[ ^R32 ]

In the general formula (III), ^R32 is a residue obtained by removing a hydroxyl group of a monohydric or higher alcohol.

  Examples of the monohydric or higher alcohol that can be used in the first to fifth embodiments include the following. Examples of the monohydric alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, 1-pentanol, 2-pentanol, isoamyl alcohol, 1-hexanol, -Saturated aliphatic alcohols such as hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol and pentadecanol, cyclohexanol, cyclopentanol and the like And unsaturated aliphatic alcohols such as allyl alcohol, butenol, hexenol and 2-hydroxyethyl acrylate.

  Examples of the dihydric alcohol include ethylene glycol, propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,6-cyclohexanediol, , 4-cyclohexanediol, methylpentanediol, cyclohexanedimethanol, methylpentanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, and the like.

  Examples of the trihydric alcohol include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-hydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, and the like. .

  Examples of the tetrahydric alcohol include sugar alcohols such as tetritol such as erythrose, pentitol such as xylitol, and hexitol such as sorbitol. Examples of the phenols include phenol, benzylphenol, o-cresol, p-cresol, catechol, ethylphenol, octylphenol, xylenol, naphthol, nonylphenol, bisphenol A and the like.

  Further, polyester polyols, polypropylene glycols, polyethylene glycols, polytetraethylene glycols and the like made from the above-mentioned alcohols are also suitable as the mono- or higher-valent alcohol of the present invention. In addition, an acrylic polyol having a hydroxyl group can also be used as a monohydric or higher alcohol.

The alcohol used in the first to fifth embodiments preferably contains a dihydric or higher alcohol from the viewpoint of improving the quick drying property of the paint. That is, in the general formula (III), R ³² is preferably a residue obtained by removing a hydroxyl group of a divalent or higher alcohol.
From the viewpoint of increasing the solubility in a low-polarity organic solvent, it is preferable to use an alcohol having 3 to 50 carbon atoms. That is, in formula (III), R ³² is preferably a residue obtained by removing the hydroxyl group of an alcohol having 3 to 50 carbon atoms. From the viewpoint of enhancing the dispersion stability when dispersed in water, it is preferable to use a monohydric alcohol having 1 to 10 carbon atoms.・ General formula (V)

〔Ｙ^１〕

一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造［−Ｃ（＝Ｏ）−Ｏ−］および／またはエーテル構造（−Ｏ−）を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。
エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基としては、−（ＣＨ_２）_ｎ１−Ｘ−（ＣＨ_２）_ｎ２−で表される基（ｎ１およびｎ２はそれぞれ独立して、０〜１０の整数である。但し、ｎ１およびｎ２の両方とも０になることはなく、ｎ１、ｎ２のうち、ＮＣＯと結合している側は１以上であることが好ましい。Ｘは、エステル基またはエーテル基である。）が挙げられる。
反応速度を速めたい場合、Ｘがエステル基であることが好ましい。
ｎ１およびｎ２は０〜４が好ましく、０〜２がより好ましい。ｎ１およびｎ２の組み合わせとしては、例えば、ｎ１＝０、ｎ２＝２の組み合わせ、ｎ１＝２、ｎ２＝２の組み合わせが好ましい。

[Y ¹ ]

In the general formula (V), a plurality of Y ¹ are each independently a single bond or a carbon which may contain an ester structure [—C (＝ O) —O—] and / or an ether structure (—O—). It is a divalent hydrocarbon group of the formulas 1 to 20. A plurality of Y ¹ may be the same or different.
Examples of the divalent hydrocarbon group having ester structure and / or carbon atoms which may contain an ether structure _{1~20, - (CH 2) n1} -X- (CH 2) n2 - group represented by (n1 and n2 Are each independently an integer from 0 to 10. However, both n1 and n2 do not become 0, and it is preferable that one of n1 and n2 bonded to NCO is 1 or more. X is an ester group or an ether group).
When it is desired to increase the reaction rate, X is preferably an ester group.
n1 and n2 are preferably 0 to 4, and more preferably 0 to 2. As a combination of n1 and n2, for example, a combination of n1 = 0 and n2 = 2, and a combination of n1 = 2 and n2 = 2 are preferable.

[R ⁵¹ ]

R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group for R ⁵¹ is not particularly limited, and includes an alkyl group, an alkenyl group, an alkynyl group, and the like. R ¹ is preferably a hydrogen atom.

It is preferable that the molecular weight of the triisocyanate that is the base of the group represented by the general formula (V) in the first to fifth embodiments is 139 or more and 1000 or less.
The lower limit of the molecular weight is preferably 139 or more, more preferably 150 or more, further preferably 180 or more, and particularly preferably 200 or more. The upper limit of the molecular weight is preferably 1,000 or less, more preferably 800 or less, further preferably 600 or less, and particularly preferably 400 or less. When the molecular weight is equal to or more than the above lower limit, crystallinity is easily suppressed. In addition, when the molecular weight is equal to or less than the above upper limit, lower viscosity can be easily achieved.

The triisocyanate that is the base of the group represented by the general formula (V) in the first to fifth embodiments has a low viscosity, so that a plurality of hydrocarbon groups in Y ¹ have an aliphatic group or an aromatic group. Is preferred. Also, R ¹ is preferably hydrogen.
Further, in order to improve the weather resistance when used as a curing agent of the coating composition, but preferably the hydrocarbon group in the plurality of Y ¹ is an aliphatic group or an alicyclic group.
In addition, it is preferable that a plurality of Y ¹ be composed of only a hydrocarbon group.
Separately, in order to maintain heat resistance, at least one of the plurality of Y ¹ preferably has an ester group.
In order to maintain hydrolysis resistance, at least one of the plurality of Y ³¹ preferably has a hydrocarbon group containing an ether structure or a hydrocarbon group.

Examples of the triisocyanate which is a source of the group represented by the general formula (V) in the first to fifth embodiments include 4-isocyanatomethyl-1,8-octaphthalate disclosed in JP-B-63-15264. Methylene diisocyanate (hereinafter referred to as NTI, molecular weight 251), 1,3,6-hexamethylene triisocyanate (hereinafter referred to as HTI, molecular weight 209) disclosed in JP-A-57-198760, Bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter referred to as GTI, molecular weight 311) disclosed in JP-A-1033, lysine triisocyanate disclosed in JP-A-53-1351931 (Hereinafter referred to as LTI, molecular weight 267).
Among these, NTI, GTI or LTI is preferable, NTI or LTI is more preferable, and LTI is particularly preferable from the viewpoint of further improving the reactivity of the isocyanate group.

Further, in order to maintain hydrolysis resistance, at least one of the plurality of Y ¹ preferably has a hydrocarbon group containing an ether structure.

The triisocyanate that is the base of the group represented by the general formula (V) in the first to fifth embodiments can be obtained by isocyanating an amino acid derivative or an amine such as an etheramine or an alkyltriamine. As the amino acid derivative, for example, 2,5-diaminovaleric acid, 2,6-diaminohexanoic acid, aspartic acid, glutamic acid and the like can be used. Since these amino acids are diamine monocarboxylic acid or monoamine dicarboxylic acid, the number of amino groups is controlled by esterifying the carboxyl group with an alkanolamine such as ethanolamine or by esterifying the carboxyl group with methanol or the like. can do. The resulting amine having an ester group can be converted to a triisocyanate or a diisocyanate containing an ester structure by phosgenation or the like.
Examples of the ether amine include “D403”, a product name of Mitsui Chemical Fine Inc., which is a polyoxyalkylene triamine. These are triamines, and can be converted into triisocyanates containing an ether structure by phosgenation of the amine or the like.
Examples of the alkyltriamine include triisocyanatononane (4-aminomethyl-1,8-octanediamine) and the like. This is a triamine, and can be converted to a triisocyanate containing only a hydrocarbon by phosgenation of the amine or the like.

In the first to fifth embodiments, the number of nitrogen elements contained in the allophanate structure is calculated based on the total number of nitrogen elements derived from isocyanate groups contained in the polyisocyanate composition. ³¹ , excluding the nitrogen element contained in R ³² ) is 1.5% or more and 60% or less. By setting the number of nitrogen elements contained in the allophanate structure in this range, the solubility in low-polarity organic solvents and the dispersibility in water are improved, and the weather resistance and water resistance of the obtained coating film are set to a high level. In addition, quick drying can be exhibited.
The range of the nitrogen element is preferably 3% or more and 50% or less, more preferably 5% or more and 40% or less, and particularly preferably 7% or more and 30% or less.

Here, the nitrogen element derived from the isocyanate group is an isocyanate group, and an isocyanate such as an allophanate structure, an isocyanurate structure, a uretdione structure, an iminooxadiazinedione structure, a urethane structure, and a buret structure, which are generated by reacting the isocyanate group. It refers to the site generated by the reaction or the site generated by the reaction between the isocyanate group and another functional group. The number of nitrogen elements derived from isocyanate groups and the ratio of nitrogen elements contained in the allophanate structure can be determined by ¹³ C-NMR. In the case where two or more different isocyanate species are contained, they may be determined by appropriately performing H-NMR measurement or NMR measurement of each component after separating the components using a liquid chromatogram or the like. Can be.
Since the peak position varies depending on the device used, the measurement conditions, and the substance used, it is desirable to appropriately determine the peak position using a standard substance or the like and calculate the ratio of each structure.

As a method of generating an allophanate structure, there are a method of heating isocyanate molecules, a method of using a catalyst, and the like. The allophanate-forming catalyst is not particularly limited, but at least one compound selected from the group consisting of a zirconyl compound represented by the following formula (XV) and a zirconium alcoholate represented by the following formula (XIX) is used. In order to obtain a polyisocyanate composition having a higher generation ratio of the allophanate structure, it is preferable to use a zirconyl compound.
The zirconyl compound is a compound having a structure represented by the following formula (XV).

［一般式（ＸＶ）中、Ｒ^６１およびＲ^６２は、それぞれ独立に、アルキルカルボニウムオキシ基、アルコキシ基、アルキル基、ハロゲン基、無機酸の水素残基である。］

[In the general formula (XV), R ⁶¹ and R ⁶² each independently represent an alkylcarboniumoxy group, an alkoxy group, an alkyl group, a halogen group, or a hydrogen residue of an inorganic acid. ]

Here, the alkylcarboniumoxy group means a residue obtained by removing hydrogen of an organic carboxylic acid. That is, when both R ⁶¹ and R ⁶² in the above formula (XV) are an alkylcarboniumoxy group, the zirconium compound is a zirconyl carboxylate. Organic carboxylic acids include aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated carboxylic acids, hydroxyl-containing carboxylic acids, halogenated alkyl carboxylic acids, and the like, as well as polybasic carboxylic acids such as dicarboxylic acids and tricarboxylic acids. .

  Specific examples of the zirconyl compound include zirconyl halide, zirconyl carboxylate, dialkyl zirconyl, zirconyl dialcolate, zirconyl carbonate, lead zirconyl sulfate, and zirconyl nitrate. Of these, zirconyl carboxylate is preferred. Examples of zirconyl carboxylate include zirconyl formate, zirconyl acetate, zirconyl propionate, zirconyl butanoate, zirconyl pentanoate, zirconyl hexanoate, zirconyl caproate, zirconyl octanoate, zirconyl 2-ethylhexanoate, zirconyl decanoate, Saturated aliphatic carboxylic acid salts such as zirconyl dodecanoate, zirconyl tetradecanoate, and zirconyl pentadecanoate; saturated cyclic carboxylic acids such as zirconyl cyclohexanecarboxylate and zirconyl cyclopentanecarboxylate; mixtures of the above carboxylate salts such as zirconyl naphthenate; olein Aliphatic zirconyl acid salts, zirconyl linoleate, zirconyl linoleate, etc., zirconyl benzoate, zirconyl toluate, zirconyl diphenylacetate, etc. Aromatic carboxylic acid salts. Among them, zirconyl naphthenate, zirconyl 2-ethylhexanoate and zirconyl acetate are particularly preferable because they are easily available industrially.

  Zirconium alcoholate is a compound having a structure represented by the following formula (XIX).

［一般式（ＩＶ）中、Ｒ^７１、Ｒ^７２、Ｒ^７３、およびＲ^７４は、それぞれ独立に、アルキル基、アルケン基、アルキン基である。］

[In the general formula (IV), R ⁷¹ , R ⁷² , R ⁷³ , and R ⁷⁴ are each independently an alkyl group, an alkene group, or an alkyne group. ]

  Examples of the raw material alcohol for zirconium alcoholate include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, 1-pentanol, 2-pentanol, isoamyl alcohol, and 1-hexanol. , 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol, saturated aliphatic alcohols such as pentadecanol, and cyclohexanol and the like Examples include cycloaliphatic alcohols, unsaturated aliphatic alcohols such as ethanal, propanal, butanal, and 2-hydroxyethyl acrylate. Also, ethylene glycol, propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,6-cyclohexanediol, 1,4-cyclohexanediol, etc. Polyhydric alcohols such as diols and triols such as glycerin can also be used. Among zirconium alcoholates, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-propoxyzirconium, and tetra-n-butoxyzirconium are preferable because they are industrially easily available.

  The allophanation reaction temperature is preferably from 60 ° C to 160 ° C, more preferably from 70 ° C to 160 ° C, and particularly preferably from 80 ° C to 160 ° C. When the content is equal to or less than the above upper limit, side reactions are less likely to occur, and coloring of the obtained polyisocyanate composition tends to be effectively prevented.

The allophanation reaction is not particularly limited, for example, by the addition of an acidic compound such as a phosphoric acid compound, sulfuric acid, nitric acid, chloroacetic acid, benzoyl chloride, a sulfonic acid ester agent, or an ion exchange resin, a chelating agent, a chelating resin or the like. Stop.
Here, examples of the phosphoric acid compound include phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, and alkyl esters thereof. In the present invention, at least one of these phosphoric acid compounds is used as a terminator. Is preferred.

The content of the polyisocyanate compound in the polyisocyanate composition of the first to fifth embodiments is preferably 5 to 100% by mass, more preferably 10 to 90% by mass, and more preferably 20 to 70% by mass. It is more preferred that there be. When the content is 5% by mass or more, the quick-drying property tends to be excellent. By setting the content to 100% or less, the viscosity can be reduced, and when workability is strongly required, the content of the polyisocyanate is preferably reduced.

Further, in addition to the polyisocyanate compound represented by the general formula (III), the polyisocyanate composition of the first to fifth embodiments has a compound having a uretdione structure, a compound having an allophanate structure, and an iminooxadiazinedione structure. , A compound having a urethane structure, and a compound having a buret structure.
The uretdione structure, allophanate structure, iminooxadiazinedione structure, urethane structure, and burette structure are represented by the following formulas (VII), (VIII), (XI), (IX), and (X), respectively. Among them, a compound having an allophanate structure, a compound having an uretdione structure, and a compound having an iminooxadiazinedione structure are preferred from the viewpoint of the penetration into the lower layer of the multilayer coating film.

The polyisocyanate composition of the first to fifth embodiments may further contain a triisocyanate represented by the following general formula (V) -1.
-General formula (V) -1

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

When the known polyisocyanate compositions are prepared from volatile diisocyanates such as, for example, 1,6-hexamethylene diisocyanate, 1,5-pentane diisocyanate, toluene diisocyanate or isophorone diisocyanate, the unreacted starting diisocyanate is finally formed, for example by distillation. It is necessary to remove from the product to less than 2% by weight, preferably less than 1% by weight based on the weight of the polyisocyanate composition. However, when the polyisocyanate composition of the first embodiment is manufactured, since the number of NCO groups of the triisocyanate used in the first embodiment is three, the polyol of the polyisocyanate composition of the first embodiment is used. It does not necessarily reduce the cross-linking ability with the polymer and does not necessarily need to be removed.
When removing unreacted triisocyanate, it can be separated from the polyisocyanate composition by a thin-film distillation method, a solvent extraction method, or the like.

  The viscosity at 25 ° C. of the polyisocyanate composition of the first to fifth embodiments is not particularly limited, but is preferably from 10 mPa · s to 300 mPa · s, more preferably from 10 mPa · s to 200 mPa · s, It is particularly preferably from 10 mPa · s to 100 mPa · s. Above the lower limit, curability tends to be excellent, and below the upper limit, workability tends to be excellent. The viscosity can be measured by using an E-type viscometer (manufactured by Tokimec).

The polyisocyanate composition of the first to fifth embodiments can be used by mixing with different isocyanate compounds and polyisocyanates obtained from these isocyanate compounds.
The different isocyanate compound is a di- or poly-isocyanate having an aliphatic, alicyclic or aromatic isocyanate group. Examples of the diisocyanate include tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane-1,6-diisocyanate, and 2-methylpentane-1,5. -Diisocyanate (MPDI), 1,3-bis (isocyanatomethyl) -cyclohexane (1,3-H6-XDI), 3 (4) -isocyanatomethyl-1-methyl-cyclohexylisoanate (IMCI); isophorone Diisocyanate (IPDI), bis (isocyanatomethyl) -norbornane (NBDI), 1,3-bis (isocyanatomethyl) -benzene, 1,3-bis (2-isocyanatopropyl-2) benzene and 4,4 '-Dicyclohexyl meta Diisocyanate (H12MDI), LDI, and the like. Among them, HDI and IPDI are preferred from the viewpoint of weather resistance and industrial availability. These diisocyanates may be used alone or in combination of two or more.
Examples of the polyisocyanate include those having an isocyanurate structure, a uretdione structure, an allophanate structure, an iminooxadiazinedione structure, a urethane structure, and a burette structure in the molecule.

[1st-6th Embodiment]

The polyisocyanate composition of the first to sixth embodiments of the present invention contains a polyisocyanate compound represented by the general formula (III).

［一般式（ＩＩＩ）中、複数あるＲ^３１は、それぞれ独立に、有機基であり、複数あるＲ^３１のうち少なくとも１つは一般式（Ｖ）で表される基、または一般式（ＶＩ）で表される基である。複数あるＲ^３１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^３２は、１価以上のアルコールから１つのヒドロキシ基を除去した残基である。］

[In general formula (III), a plurality of R ³¹ are each independently an organic group, and at least one of the plurality of R ³¹ is a group represented by general formula (V) or a general formula (VI) Is a group represented by A plurality of R ³¹ may be the same or different. R ³² is a residue obtained by removing one hydroxy group from a monovalent or higher alcohol. ]

［一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。波線は結合手を意味する。］

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

［一般式（ＶＩ）中、Ｙ^２はエステル構造を含む炭素数１〜２０の２価の炭化水素基である。波線は結合手を意味する。］
以下、一般式（ＩＩＩ）、一般式（Ｖ）、および一般式（ＶＩ）について説明する。

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond. ]
Hereinafter, general formulas (III), (V), and (VI) will be described.

・ General formula (III)

一般式（ＩＩＩ）で表されるポリイソシアネート化合物は、アロファネート構造を有する。アロファネート構造は２つのイソシアネート基と、１つのヒドロキシ基とからなる結合構造である。

The polyisocyanate compound represented by the general formula (III) has an allophanate structure. The allophanate structure is a bonding structure composed of two isocyanate groups and one hydroxy group.

[R ³¹ ]

In the general formula (III), a plurality of R ³¹ are each independently an organic group. A plurality of R ³¹ may be the same or different.
In the first to sixth embodiments, at least one of the two R ³¹ is a group represented by the general formula (V) or a group represented by the general formula (VI), It is preferred that ³¹ is a group represented by the general formula (V) or a group represented by the general formula (VI).

Examples of the group other than the group represented by the following general formula (V) or the following general formula (VI) among R ³¹ include, for example, tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI ), 2,2,4-trimethylhexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate (MPDI), 1,3-bis (isocyanatomethyl) -cyclohexane (1,3-H6- XDI), 3 (4) -isocyanatomethyl-1-methyl-cyclohexyl isocyanate (IMCI); isophorone diisocyanate (IPDI), bis (isocyanatomethyl) -norbornane (NBDI), 1,3-bis (isocyanato Methyl) -benzene, 1,3-bis (2-isocyanatotop Roppyl-2) a residue obtained by removing one isocyanate group from benzene and 4,4′-dicyclohexylmethane diisocyanate (H12MDI).

[ ^R32 ]

In the general formula (III), R ³² is a residue obtained by removing one hydroxyl group from monovalent or polyvalent alcohols.
More specifically, R ³² is, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, 1-pentanol, 2-pentanol, isoamyl alcohol, -Saturated aliphatic alcohols such as hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol and pentadecanol, cyclohexanol, It is a residue obtained by removing one hydroxy group from a monohydric alcohol such as an unsaturated aliphatic alcohol such as a saturated cyclic aliphatic alcohol such as cyclopentanol, allyl alcohol, butenol, hexenol, or 2-hydroxyethyl acrylate.

For example, ethylene glycol, propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,6-cyclohexanediol, 1,4-cyclohexanediol, A residue obtained by removing one hydroxy group from a dihydric alcohol such as methylpentanediol, cyclohexanedimethanol, methylpentanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, etc. .
For example, one hydroxyl group is formed from a trihydric alcohol such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-hydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol. This is the residue from which the group has been removed.
For example, it is a residue obtained by removing one hydroxy group from a tetrahydric alcohol such as sugar alcohol such as pentitol such as erythrose and pentitol such as xylitol and hexitol such as sorbitol.
For example, it is a residue obtained by removing one hydroxy group from phenols such as phenol, benzylphenol, o-cresol, p-cresol, catechol, ethylphenol, octylphenol, xylenol, naphthol, nonylphenol and bisphenol A.
For example, a residue obtained by removing one hydroxy group from an alcohol such as polyester polyol, polypropylene glycol, polyethylene glycol, or polytetraethylene glycol using the above-mentioned alcohol as a raw material may be used.
For example, it may be a residue obtained by removing one hydroxy group from an acrylic polyol having a hydroxyl group.・ General formula (V)

［Ｙ^１］

一般式（Ｖ）中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造［−Ｃ（＝Ｏ）−Ｏ−］および／またはエーテル構造（−Ｏ−）を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。但し、複数あるＹ^１のうち少なくとも１つは、エステル構造を含む。
エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基としては、−（ＣＨ_２）_ｎ１−Ｘ−（ＣＨ_２）_ｎ２−で表される基（ｎ１およびｎ２はそれぞれ独立して、０〜１０の整数である。但し、ｎ１およびｎ２の両方とも０になることはなく、ｎ１、ｎ２のうち、ＮＣＯと結合している側は１以上であることが好ましい。Ｘは、エステル基またはエーテル基である。）が挙げられる。
反応速度を速めたい場合、Ｘがエステル基であることが好ましい。
ｎ１およびｎ２は０〜４が好ましく、０〜２がより好ましい。ｎ１およびｎ２の組み合わせとしては、例えば、ｎ１＝０、ｎ２＝２の組み合わせ、ｎ１＝２、ｎ２＝２の組み合わせが好ましい。

[Y ¹ ]

In the general formula (V), a plurality of Y ¹ are each independently a single bond or a carbon which may contain an ester structure [—C (＝ O) —O—] and / or an ether structure (—O—). It is a divalent hydrocarbon group of the formulas 1 to 20. A plurality of Y ¹ may be the same or different. However, at least ^one of the plurality of Y ¹ includes an ester structure.
Examples of the divalent hydrocarbon group having ester structure and / or carbon atoms which may contain an ether structure _{1~20, - (CH 2) n1} -X- (CH 2) n2 - group represented by (n1 and n2 Are each independently an integer from 0 to 10. However, both n1 and n2 do not become 0, and it is preferable that one of n1 and n2 bonded to NCO is 1 or more. X is an ester group or an ether group).
When it is desired to increase the reaction rate, X is preferably an ester group.
n1 and n2 are preferably 0 to 4, and more preferably 0 to 2. As a combination of n1 and n2, for example, a combination of n1 = 0 and n2 = 2, and a combination of n1 = 2 and n2 = 2 are preferable.

[ ^R51 ]

R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group for R ⁵¹ is not particularly limited, and includes an alkyl group, an alkenyl group, an alkynyl group, and the like. As R ⁵¹ , a hydrogen atom is preferable.

It is preferable that the molecular weight of the triisocyanate that is the base of the group represented by the general formula (V) in the first to sixth embodiments is 139 or more and 1000 or less.
The lower limit of the molecular weight is preferably 139 or more, more preferably 150 or more, further preferably 180 or more, and particularly preferably 200 or more. The upper limit of the molecular weight is preferably 1,000 or less, more preferably 800 or less, further preferably 600 or less, and particularly preferably 400 or less. When the molecular weight is equal to or more than the above lower limit, crystallinity is easily suppressed. In addition, when the molecular weight is equal to or less than the above upper limit, lower viscosity can be easily achieved.

The triisocyanate that is the base of the group represented by the general formula (V) in the first to sixth embodiments has a low viscosity, so that a plurality of hydrocarbon groups in Y ¹ have an aliphatic group or an aromatic group. Is preferred. Also, R ⁵¹ is preferably hydrogen.
Further, in order to improve the weather resistance when used as a curing agent of the coating composition, but preferably the hydrocarbon group in the plurality of Y ¹ is an aliphatic group or an alicyclic group.
Separately, in order to maintain heat resistance, at least one of the plurality of Y ¹ preferably has an ester group.

Examples of the triisocyanate that is a source of the group represented by the general formula (V) in the first to sixth embodiments include bis (2-isocyanatoethyl) 2- disclosed in Japanese Patent Publication No. 4-1033. Examples thereof include isocyanatoglutarate (hereinafter, referred to as GTI, molecular weight 311) and lysine triisocyanate (hereinafter, referred to as LTI, molecular weight 267) disclosed in JP-A-53-135931.
Among these, LTI is particularly preferred from the viewpoint of further improving the reactivity of the isocyanate group.

Further, in order to maintain hydrolysis resistance, at least one of the plurality of Y ¹ preferably has a hydrocarbon group containing an ether structure. -General formula (VI)

［Ｙ^２］

一般式（ＶＩ）中、Ｙ^２はエステル構造を含む炭素数１〜２０の２価の炭化水素基である。

[Y ² ]

In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and containing an ester structure.

The diisocyanate, which is the base of the group represented by the general formula (VI) in the first to sixth embodiments, has an ester structure in order to increase the reactivity of the isocyanate group when used as a curing agent for the coating composition.
Further, the hydrocarbon group in Y ² preferably has an aliphatic group or an aromatic group in the structure in order to have a low viscosity. In order to maintain heat resistance, Y ² is a hydrocarbon group having an ester structure. It is preferable to have
Examples of this category include lysine diisocyanate (hereinafter, LDI).

  In the first to sixth embodiments, the triisocyanate as the base of the group represented by the general formula (V) or the diisocyanate as the base of the group represented by the general formula (VI) is obtained by converting an amine such as an amino acid derivative into isocyanate. Obtainable. As the amino acid derivative, for example, 2,5-diaminovaleric acid, 2,6-diaminohexanoic acid, aspartic acid, glutamic acid and the like can be used. Since these amino acids are diamine monocarboxylic acid or monoamine dicarboxylic acid, the number of amino groups is controlled by esterifying the carboxyl group with an alkanolamine such as ethanolamine or by esterifying the carboxyl group with methanol or the like. can do. The resulting amine having an ester group can be converted to a triisocyanate or a diisocyanate containing an ester structure by phosgenation or the like.

As a method for generating the allophanate structure, there are a heating method, a method using a catalyst, and the like. The allophanate-forming catalyst is not particularly limited, and uses at least one compound selected from the group consisting of a zirconyl compound represented by the following general formula (XV) and a zirconium alcoholate represented by the following general formula (XIX) I do. In order to obtain a polyisocyanate composition having a higher generation ratio of allophanate groups, it is preferable to use a zirconyl compound.
The zirconyl compound is a compound having a structure represented by the following general formula (XV).

[In the general formula (XV), R ⁶¹ and R ⁶² each independently represent an alkylcarboniumoxy group, an alkoxy group, an alkyl group, a halogen group, or a hydrogen residue of an inorganic acid. ]

In the present specification, the “alkylcarboniumoxy group” means a residue obtained by removing hydrogen of an organic carboxylic acid. That is, when both R ⁶¹ and R ^{62 in} the general formula (XV) are alkylcarboniumoxy groups, the zirconium compound is a zirconyl carboxylate.
Examples of the organic carboxylic acid include, for example, aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated carboxylic acids, hydroxyl-containing carboxylic acids, halogenated alkyl carboxylic acids, and the like, as well as dicarboxylic acids, tricarboxylic acids, and other polybasic carboxylic acids. Also includes acids.

  Specific examples of the zirconyl compound include zirconyl halide, zirconyl carboxylate, dialkyl zirconyl, zirconyl dialcolate, zirconyl carbonate, lead zirconyl sulfate, and zirconyl nitrate. Among them, zirconyl carboxylate is preferred. Examples of zirconyl carboxylate include zirconyl formate, zirconyl acetate, zirconyl propionate, zirconyl butanoate, zirconyl pentanoate, zirconyl hexanoate, zirconyl caproate, zirconyl octanoate, zirconyl 2-ethylhexanoate, zirconyl decanoate, Saturated aliphatic carboxylic acid salts such as zirconyl dodecanoate, zirconyl tetradecanoate, and zirconyl pentadecanoate; saturated cyclic carboxylic acids such as zirconyl cyclohexanecarboxylate and zirconyl cyclopentanecarboxylate; mixtures of the above carboxylate salts such as zirconyl naphthenate; olein Aliphatic zirconyl acid salts, zirconyl linoleate, zirconyl linoleate, etc., zirconyl benzoate, zirconyl toluate, zirconyl diphenylacetate, etc. Aromatic carboxylic acid salts. Among them, zirconyl compounds, zirconyl naphthenate, zirconyl 2-ethylhexanoate, and zirconyl acetate are particularly preferable from the viewpoint of industrial availability.

  Zirconium alcoholate is a compound having a structure represented by the following general formula (XIX).

[In the general formula (XIX), R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ are each independently an alkyl group, an alkene group, or an alkyne group. ]

Examples of the alcohol used as a raw material of zirconium alcoholate include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, 1-pentanol, 2-pentanol, isoamyl alcohol, -Saturated aliphatic alcohols such as hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol and pentadecanol, cyclohexanol and the like And unsaturated aliphatic alcohols such as ethanal, propanal, butanal and 2-hydroxyethyl acrylate. Also, ethylene glycol, propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,6-cyclohexanediol, 1,4-cyclohexanediol, etc. Polyhydric alcohols such as diols and triols such as glycerin can also be used.
Among them, as the zirconium alcoholate, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-propoxyzirconium, and tetra-n-butoxyzirconium are preferable from the viewpoint of industrial availability.

The allophanation reaction temperature is preferably from 60 ° C to 160 ° C, more preferably from 70 ° C to 160 ° C, even more preferably from 80 ° C to 160 ° C. When the content is equal to or less than the above upper limit, side reactions are less likely to occur, and coloring of the obtained polyisocyanate composition tends to be effectively prevented.
The allophanation reaction is not particularly limited, for example, by the addition of an acidic compound such as a phosphoric acid compound, sulfuric acid, nitric acid, chloroacetic acid, benzoyl chloride, a sulfonic acid ester agent, or an ion exchange resin, a chelating agent, a chelating resin or the like. Stop.
Here, examples of the phosphoric acid compound include phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, and alkyl esters thereof. In the first to sixth embodiments, at least one kind of these phosphoric acid compounds is used. Is preferably used as a terminator.
The conversion of the polyisocyanate composition of the first to sixth embodiments is preferably 1% or more and 100% or less, more preferably 10% or more and 80% or less, and particularly preferably 20% or more and 70% or less. Above the lower limit, the curability tends to be excellent, and below the upper limit, the viscosity tends to be low and the workability tends to be excellent.

  The conversion was determined by gel permeation chromatography (hereinafter referred to as "GPC"), and the area ratio of the peak having a number average molecular weight larger than that of the unreacted triisocyanate was determined by the number average molecular weight based on polystyrene.

  The content of the polyisocyanate compound in the polyisocyanate composition of the first to sixth embodiments is preferably from 1% by mass to 100% by mass, more preferably from 10% by mass to 90% by mass, More preferably, it is 20% by mass or more and 80% by mass or less. When it is at least the above lower limit, drying properties tend to be excellent, and when it is at most the above upper limit, viscosity tends to be low and workability tends to be excellent.

Further, in addition to the polyisocyanate compound represented by the formula (III), a compound having an isocyanurate structure, a compound having a uretdione structure, an iminooxadiazinedione, A compound having a structure, a compound having a urethane structure, and a compound having a buret structure may be included.
The isocyanurate structure, uretdione structure, iminooxadiazinedione structure, urethane structure, and burette structure are represented by the following formulas (XII), (VII), (XI), (IX), and (X), respectively. Among them, a compound having an isocyanurate structure, a compound having a uretdione structure, or a compound having an iminooxadiazinedione structure is preferable from the viewpoint of coating film hardness.

In the polyisocyanate compound contained in the polyisocyanate composition of Embodiment 1-6, the molar ratios of the allophanate structure, the uretdione structure, the iminooxadiazinedione structure, the isocyanurate structure, the urethane structure, and the buret structure are represented by a and b. , C, d, e, and f, the molar ratio of the allophanate structure (a / (a + b + c + d + e + f)) is preferably 0.02 or more and 0.95 or less.
From the viewpoint of solubility in low-polarity organic solvents, the lower limit of the ratio is preferably 0.02 or more, more preferably 0.05 or more, and particularly preferably 0.10 or more. The upper limit of the ratio is preferably 0.95 or less, more preferably 0.90 or less, from the viewpoint of drying properties.

The polyisocyanate composition of the first to sixth embodiments has a reaction rate ( ^Vh ) between the polyisocyanate composition and the primary alcohol, which is higher than the reaction rate (Vh) between the polyisocyanate derived from hexamethylene diisocyanate and the primary alcohol. the ratio of ^{p) (V h / V p} ) is preferably less than 5 or 13.

Ratio of the reaction rate (V ^p ) between the polyisocyanate composition of the first to sixth embodiments and the primary alcohol (V ^p ) to the reaction rate (V ^h ) between the polyisocyanate derived from hexamethylene diisocyanate and the primary alcohol ( ( ^Vh / ^Vp ) is preferably greater than 1 and more preferably 5 or more from the viewpoint of drying property of the coating film. Further, from the viewpoint of the pot life of the coating material, it is preferably less than 15, more preferably less than 13.
The upper limit and the lower limit can be arbitrarily combined, but are preferably 5 or more and less than 13 in the first to sixth embodiments.

The reaction rate between the polyisocyanate composition and the primary alcohol can be measured, for example, by the following method.
The polyisocyanate composition is mixed so that the molar ratio of the NCO group to the OH group of the primary alcohol becomes 1, heated and stirred at 70 ° C., the residual rate of the NCO group is measured, and the rate of decrease is defined as the reaction rate. The residual ratio of NCO groups can be determined, for example, by measuring the NCO content.

  Examples of the primary alcohol include 1-butanol, iso-butanol, 2-ethylhexanol and the like. Examples of the polyisocyanate derived from hexamethylene diisocyanate include “Duranate TKA-100” and “Duranate TPA-100” (trade names) of Asahi Kasei Corporation.

  The polyisocyanate composition according to the first to sixth embodiments can be prepared, for example, by the following method: 1) a method of producing the above-mentioned triisocyanate by isocyanuration; There is a method in which a group is produced by reacting a group with a thermal dissociating agent, performing isocyanuration, and then dissociating the thermal dissociating agent by heating or the like. Examples of the thermal dissociating agent include methyl ethyl ketoxime. In the production method (2), a polyisocyanate composition having a high reaction rate between the polyisocyanate composition and the primary alcohol can be obtained, which is preferable from the viewpoint of quick drying of the coating.

The polyisocyanate composition of the first to sixth embodiments preferably further contains a triisocyanate represented by the following general formula (V) -1 or a diisocyanate represented by the following general formula (VI) -1. -General formula (V) -1

［一般式（Ｖ）−１中、複数あるＹ^１は、それぞれ独立に、単結合、あるいは、エステル構造および／またはエーテル構造を含んでもよい炭素数１〜２０の２価の炭化水素基である。複数あるＹ^１は、それぞれ同一であってもよく異なっていてもよい。Ｒ^５１は、水素原子または炭素数１〜１２の１価の炭化水素基である。］〔Ｒ^５１、Ｙ^１〕

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ] ^[R 51, ^{Y 1]}

Description of the general formula (V) ^R 51, ^{Y 1} in the -1 is the same as the description of ^R 51, ^{Y 1} in the general formula (V).
However, in the general formula (V) -1, Y ¹ may or may not contain an ester structure and / or an ether structure. In the first to sixth embodiments, at least one of the plurality of Y ²¹ preferably contains an ester structure and / or an ether structure.
In general formula (V) ^R 51, ^{Y 1} in the -1, ^R 51, ^{Y 1} and may be different may be the same in the general formula (V). -General formula (VI) -1

［一般式（ＶＩ）−１中、Ｙ^２はエステル構造を含んでいてもよい炭素数１〜２０の２価の炭化水素基である。］〔Ｙ^２〕

一般式（ＶＩ）−１中のＹ^２に関する説明は、前記一般式（ＶＩ）中のＹ^２に関する説明と同様である。
ただし、一般式（ＶＩ）−１においては、Ｙ^２はエステル構造および／またはエーテル構造を含んでもよく、含んでいなくてもよい。第１−６実施形態においては、Ｙ^２はエステル構造および／またはエーテル構造を含むことが好ましい。
また、一般式（ＶＩ）−１中のＹ^２は、前記一般式（ＶＩ）中のＹ^２と同一であってもよく異なっていてもよい。

[In general formula (VI) -1, Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ester structure. ] [Y ² ]

Description of the general formula (VI) in -1 ^{Y 2} are the same as the description of ^{Y 2} in the general formula (VI).
However, in the general formula (VI) -1, Y ² may or may not contain an ester structure and / or an ether structure. In the first to sixth embodiments, Y ² preferably contains an ester structure and / or an ether structure.
Further, Y ² in the general formula (VI) -1 may be the same as or different from Y ² in the general formula (VI).

When made from known polyisocyanate compositions, for example volatile diisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentane diisocyanate, toluene diisocyanate or isophorone diisocyanate, the unreacted starting diisocyanate is finally formed, for example by distillation. It is necessary to remove from the product to less than 2% by weight, preferably less than 1% by weight based on the weight of the polyisocyanate composition. However, when the polyisocyanate composition of the first embodiment is manufactured, since the number of NCO groups of the triisocyanate used in the first embodiment is 3, the polyol of the polyisocyanate composition of the first embodiment is used. It does not necessarily reduce the cross-linking ability with the polymer and does not necessarily need to be removed.
When removing unreacted triisocyanate, it can be separated from the polyisocyanate composition by a thin-film distillation method, a solvent extraction method, or the like.

  The viscosity at 25 ° C. of the polyisocyanate composition of the first to sixth embodiments is not particularly limited, but is preferably from 10 mPa · s to 1,000 mPa · s, more preferably from 10 mPa · s to 500 mPa · sm, It is particularly preferably from 10 mPa · s to 90 mPa · sm. Above the lower limit, curability tends to be excellent, and below the upper limit, workability tends to be excellent. The viscosity can be measured by using an E-type viscometer (manufactured by Tokimec).

<Block polyisocyanate composition>

The polyisocyanate composition of the present invention can be a blocked polyisocyanate composition by protecting an isocyanate group with a blocking agent. Examples of the blocking agent include alcohols, alkylphenols, phenols, active methylene, mercaptans, acid amides, acid imides, imidazoles, ureas, oximes, amines, imides, and pyrazole compounds. No. Examples of more specific blocking agents are shown below. (1) alcohols: alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol;
(2) Alkylphenols: mono- and dialkylphenols having an alkyl group having 4 or more carbon atoms as a substituent, for example, n-propylphenol, iso-propylphenol, n-butylphenol, sec-butylphenol, t-butylphenol , N-hexylphenol, 2-ethylhexylphenol, n-octylphenol, monoalkylphenols such as n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-t-butylphenol, Dialkylphenols such as -sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, and di-n-nonylphenol;
(3) phenol type; phenol, cresol, ethyl phenol, styrenated phenol, hydroxybenzoate, etc.

(4) Active methylene type: dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.
(5) mercaptans; butyl mercaptan, dodecyl mercaptan, etc.
(6) acid amides; acetanilide, acetate amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.
(7) acid imides; succinimide, maleic imide, etc.
(8) imidazoles; imidazole, 2-methylimidazole, etc.
(9) Urea type: urea, thiourea, ethylene urea, etc.
(10) oxime type: formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc.
(11) amine type: diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine, etc.
(12) imines; ethyleneimine, polyethyleneimine, etc.
(13) bisulfite; sodium bisulfite, etc.
(14) pyrazoles; pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, etc.
(15) Triazole type: 3,5-dimethyl-1,2,4-triazole and the like.

  The blocking reaction between the polyisocyanate composition and the blocking agent can be performed regardless of the presence or absence of a solvent. When a solvent is used, it is necessary to use a solvent inert to isocyanate groups. At the time of the blocking reaction, an organic metal salt such as tin, zinc or lead, a tertiary amine compound, an alcoholate of an alkali metal such as sodium or the like may be used as a catalyst. The reaction can be generally carried out at -20 ° C to 150 ° C, but preferably at 30 ° C to 100 ° C. Above the lower limit, the reaction rate tends to increase, and below the upper limit, side reactions do not tend to occur.

  Among the above-mentioned blocking agents, from the viewpoints of availability and viscosity of the manufactured blocked polyisocyanate composition, reaction temperature, and reaction time, oxime compounds, acid amide compounds, amine compounds, active methylene compounds, and It preferably contains at least one member selected from the group consisting of pyrazole compounds, more preferably methyl ethyl ketoxime, ε-caprolactam, diethyl malonate, ethyl acetoacetate, diisopropylamine, or 3,5-dimethylpyrazole, and methyl ethyl ketoxime. Diisopropylamine or 3,5-dimethylpyrazole is more preferred, and 3,5-dimethylpyrazole is particularly preferred from the viewpoint of achieving both low-temperature curability and compatibility with the polyol. The heat dissociable blocking agents may be used alone or in combination of two or more.

<Hydrophilic polyisocyanate composition>

The polyisocyanate composition of the present invention is obtained by reacting a compound containing an active hydrogen group and a hydrophilic group (hydrophilic group-containing compound) with an isocyanate group to form a hydrophilic polyisocyanate composition having a hydrophilic group added. it can.

The hydrophilic group-containing compound capable of reacting with the isocyanate group is not particularly limited, and examples thereof include compounds containing a nonionic, cationic, anionic or other hydrophilic group.
The compound for introducing a nonionic hydrophilic group is not particularly limited, and examples thereof include a compound in which ethylene oxide is added to a hydroxyl group of an alcohol such as methanol, ethanol, butanol, ethylene glycol, and diethylene glycol. These have active hydrogens that react with isocyanate groups. Among these, monoalcohols that can improve the water dispersibility of the hydrophilic polyisocyanate composition with a small amount of use are preferable. The number of added ethylene oxides is preferably 4 or more and 30 or less, more preferably 4 or more and 20 or less. When the number of additions of ethylene oxide is 4 or more, it tends to be easily made aqueous. Further, when the number of added ethylene oxide is 30 or less, a precipitate of the hydrophilic polyisocyanate composition tends to hardly occur during low-temperature storage.

  The introduction of the cationic hydrophilic group can be performed by a method using a compound having both a cationic group and a functional group having hydrogen which reacts with the isocyanate group, or by adding a functional group such as a glycidyl group to the isocyanate group in advance. Then, there is a method of reacting this functional group with a specific compound such as sulfide or phosphine. Among them, a method using a compound having both a cationic group and hydrogen reacting with an isocyanate group is easy.

The functional group having hydrogen that reacts with the isocyanate group is not particularly limited, and examples thereof include a hydroxyl group and a thiol group. The compound having both the cationic hydrophilic group and a functional group having a hydrogen that reacts with an isocyanate group is not particularly limited. For example, dimethylethanolamine, diethylethanolamine, diethanolamine, methyldiethanolamine, N, N-dimethyl Aminohexanol, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-N- (dimethylaminopropyl) aminoethanol No. Further, the tertiary amino group (cationic hydrophilic group) introduced into the aqueous blocked polyisocyanate can be quaternized with dimethyl sulfate, diethyl sulfate or the like.
Among them, a tertiary amino group is preferable as the cationic hydrophilic group. When the hydrophilic polyisocyanate composition has a tertiary amino group, compounds such as an anionic compound used for neutralization described later are easily volatilized by heating, and as a result, the water resistance tends to be further improved.
The introduction of the cationic hydrophilic group can be performed in the presence of a solvent. In this case, the solvent preferably does not contain a functional group capable of reacting with an isocyanate group. These solvents are not particularly restricted but include, for example, ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether and the like.

It is preferable that the cationic hydrophilic group introduced into the hydrophilic polyisocyanate composition is neutralized by a compound having an anionic group.
The anionic group is not particularly limited, and examples thereof include a carboxyl group, a sulfonic group, a phosphoric group, a halogen group, and a sulfate group.
The compound having a carboxyl group is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, and lactic acid.
The compound having a sulfone group is not particularly limited, but includes, for example, ethanesulfonic acid.
The compound having a phosphate group is not particularly limited, and examples thereof include phosphoric acid and acidic phosphates.
Further, the compound having a halogen group is not particularly limited, and examples thereof include hydrochloric acid.
The compound having a sulfate group is not particularly limited, and examples thereof include sulfuric acid.
Among them, as the compound having an anionic group, a compound having one carboxyl group is preferable, and acetic acid, propionic acid, or butyric acid is more preferable.

  Although it does not specifically limit as an anionic hydrophilic group, For example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a halogen group, a sulfate group, etc. are mentioned. The blocked polyisocyanate having an anionic hydrophilic group is obtained, for example, by reacting active hydrogen of a compound having both an anionic group and an active hydrogen that reacts with an isocyanate group, with an isocyanate group of a precursor polyisocyanate composition. be able to.

  Examples of the compound having an active hydrogen and a carboxylic acid group include, but are not particularly limited to, monohydroxy acids such as 1-hydroxyacetic acid, 3-hydroxypropanoic acid, 12-hydroxy-9-octadecanoic acid, hydroxypivalic acid, and lactic acid. Carboxylic acids; polyhydroxycarboxylic acids such as dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid and dimethylolpropionic acid. Of these, hydroxypivalic acid or dimethylolpropionic acid is preferred as the compound having active hydrogen and a carboxylic acid group.

  The compound having active hydrogen and a carboxylic acid group is not particularly limited, and examples thereof include isethionic acid.

The anionic hydrophilic group introduced into the hydrophilic polyisocyanate composition is not particularly limited, but can be neutralized with, for example, an amine compound which is a basic substance.
Examples of the amine compound include, but are not particularly limited to, ammonia and a water-soluble amino compound.
Examples of the water-soluble amino compound include, but are not limited to, monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, and the like. -Primary or secondary amines such as ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine and morpholine; and tertiary amines such as triethylamine and dimethylethanolamine.

The polyisocyanate composition of the present invention can be used by mixing with different isocyanate compounds.
The isocyanate compound of the present invention is a di-isocyanate or a poly-isocyanate having an aliphatic, alicyclic, or aromatic isocyanate group. Examples of the diisocyanate include tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane-1,6-diisocyanate, 2-methylpentane-1, 5-diisocyanate (MPDI), 1,3-bis (isocyanatomethyl) -cyclohexane (1,3-H6-XDI), 3 (4) -isocyanatomethyl-1-methyl-cyclohexylisoanate (IMCI); Isophorone diisocyanate (IPDI), bis (isocyanatomethyl) -norbornane (NBDI), 1,3-bis (isocyanatomethyl) -benzene, 1,3-bis (2-isocyanatopropyl-2) benzene and 4,4 '-Dicyclohexyl meta And diisocyanate (H12MDI) and lysine diisocyanate (LDI). Among them, HDI or IPDI is preferable from the viewpoint of weather resistance and industrial availability. These diisocyanates may be used alone or in combination of two or more.
The polyisocyanate is obtained by polymerizing the diisocyanate by using a catalyst or by heating, and has an isocyanurate structure, a uretdione structure, an allophanate structure, an iminooxadiazinedione structure, a urethane structure, a buret in a molecule. The structure is included. Among them, those having an isocyanurate structure are preferable from the viewpoint of weather resistance.

<Other compounds>

The polyisocyanate composition of the present invention comprises at least one compound selected from the group consisting of an unsaturated bond-containing compound, an inert compound, a metal atom, a basic amino compound, and carbon dioxide, based on the polyisocyanate compound. It is preferably contained in an amount of not less than 0.0 ppm by mass and not more than 1.0 × 10 ⁴ ppm by mass from the viewpoint of preventing coloring during long-term storage and improving long-term storage stability. The lower limit of the range of the content is more preferably 3.0 mass ppm or more, still more preferably 5.0 mass ppm or more, even more preferably 10 mass ppm or more. Is more preferably 5.0 × 10 ³ mass ppm or less, further preferably 3.0 × 10 ³ mass ppm or less, and more preferably 1.0 × 10 ³ mass ppm or less. Is even more preferred.

The unsaturated bond-containing compound of the present invention is preferably a compound in which the unsaturated bond is a carbon-carbon unsaturated bond, a carbon-nitrogen unsaturated bond, or a carbon-oxygen unsaturated bond. is there. From the viewpoint of the stability of the compound, the unsaturated bond is preferably a compound having a double bond, and a carbon-carbon double bond (C = C) or a carbon-oxygen double bond (C = O) is preferred. More preferred. Further, the carbon atom constituting the compound is preferably bonded to three or more atoms.
In general, the carbon-carbon double bond may be a carbon-carbon double bond constituting an aromatic ring, but the unsaturated bond contained in the unsaturated bond-containing compound of the present invention may be an aromatic bond. It does not include the carbon-carbon double bond constituting the ring.
Examples of the compound having a carbon-oxygen double bond include a carbonic acid derivative. Examples of the carbonic acid derivative include a urea compound, a carbonic acid ester, an N-unsubstituted carbamic acid ester, an N-substituted carbamic acid ester, and the like.

The inactive compounds of the present invention are classified into the following compounds A to G.
The hydrocarbon compounds are compounds A and B, the ether compounds and sulfide compounds are compounds CE below, the halogenated hydrocarbon compounds are compounds F below, silicon-containing hydrocarbon compounds, silicon-containing ether compounds, and silicon-containing sulfides. The compounds are classified into the following compounds G, respectively. The compounds A to G described herein do not contain an unsaturated bond other than the aromatic ring, and do not include the above-mentioned compounds having an unsaturated bond.
Compound A: an aliphatic hydrocarbon compound having a linear, branched or cyclic structure.
Compound B: an aromatic hydrocarbon compound which may be substituted with an aliphatic hydrocarbon group.
Compound C: a compound having an ether bond or a sulfide bond and an aliphatic hydrocarbon group, wherein the same or different aliphatic hydrocarbon compounds are bonded via an ether bond or a sulfide bond.
Compound D: a compound having an ether bond or a sulfide bond and an aromatic hydrocarbon group, wherein the same or different aromatic hydrocarbon compounds are bonded via an ether bond or a sulfide bond.
Compound E: a compound having an ether bond or a sulfide bond, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group.
Compound F: a halide in which at least one hydrogen atom constituting an aliphatic hydrocarbon compound or at least one hydrogen atom constituting an aromatic hydrocarbon compound is substituted with a halogen atom.
Compound G: a compound in which some or all of the carbon atoms of Compounds A to E have been substituted with silicon atoms.

  The metal atom of the present invention may exist as a metal ion or as a single metal atom. One kind of metal atom may be used, or a plurality of kinds of metal atoms may be combined. As the metal atom, a metal atom which can have a divalent to tetravalent valence is preferable, and among them, one or more metals selected from iron, cobalt, nickel, zinc, tin, copper, and titanium are more preferable. .

  The basic amino compound of the present invention is a derivative of ammonia, a compound in which one hydrogen is substituted by an alkyl group or an aryl group (primary), a compound in which two hydrogens are substituted (secondary), and three Are also substituted (tertiary) compounds. Basic amino compounds that can be preferably used in the present invention are secondary and tertiary amino compounds, and aliphatic amines, aromatic amines, heterocyclic amines, and basic amino acids can be preferably used.

  Carbon dioxide may be dissolved in polyisocyanate at normal pressure, or may be dissolved in a pressurized state in a pressure vessel. Since the use of carbon dioxide containing water may cause hydrolysis of the polyisocyanate compound, the amount of water contained in carbon dioxide is preferably controlled as necessary.

The halogen atom content of the polyisocyanate composition of the present invention is preferably 1.0 × 10 ² mass ppm or less from the viewpoint of preventing coloring. The halogen atom is not particularly limited, but is preferably chlorine and / or bromine, and is at least one ion and / or compound selected from chloride ion, bromine ion, hydrolysable chlorine, and hydrolysable bromine. Is more preferred. Examples of the hydrolyzed chlorine include a carbamoyl chloride compound in which hydrogen chloride is added to an isocyanate group, and examples of the hydrolyzable bromine include a carbamoyl bromide compound in which hydrogen bromide is added to an isocyanate group.

<Coating composition>

The polyisocyanate composition of the present invention can also be suitably used as a curing agent or the like for a coating composition. That is, a coating composition containing the polyisocyanate composition of the present invention can be obtained. As a resin component of the coating composition, it is preferable to include a compound having two or more active hydrogens having a reactivity with an isocyanate group in a molecule. Examples of the compound having two or more active hydrogens in the molecule include a polyol, a polyamine, and a polythiol. Among these, polyols are preferred. Specific examples of the polyol include polyester polyol, polyether polyol, acrylic polyol, polyolefin polyol, and fluorine polyol.

The coating composition using the polyisocyanate composition of the present invention can be used both in a solvent base and an aqueous base.
In the case of a solvent-based coating composition, a resin containing a compound having two or more active hydrogens in the molecule, or a solvent dilution thereof, if necessary, other resins, catalysts, pigments, leveling agents, Antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, to those to which additives such as surfactants are added, the polyisocyanate composition of the present invention is added as a curing agent, and if necessary, a solvent is further added. After adding and adjusting the viscosity, the mixture can be stirred manually or with a stirrer such as Magellar to obtain a solvent-based coating composition.

  When a water-based coating composition is used, an aqueous dispersion of a resin containing a compound having two or more active hydrogens in a molecule or a water-soluble substance may be added to another resin, a catalyst, a pigment, and a leveling agent as necessary. Agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, additives such as surfactants, to the added polyisocyanate composition of the present invention as a curing agent, if necessary, water After further adding a solvent and a solvent, the mixture is forcibly stirred by a stirrer to obtain a water-based coating composition.

  Examples of the polyester polyol include, for example, succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and dibasic acids such as carboxylic acids such as 1,4-cyclohexanedicarboxylic acid alone or Mixture with ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol , Or a mixture of polyhydric alcohols such as ethoxylated trimethylolpropane, alone or in a mixture. For example, a condensation reaction can be performed by combining the above components and heating at about 160-220 ° C. Further, for example, polycaprolactones and the like obtained by ring-opening polymerization of lactones such as ε-caprolactone using a polyhydric alcohol can also be used as the polyester polyol. These polyester polyols can be modified with aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates obtained therefrom. In this case, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates obtained therefrom are particularly preferred from the viewpoints of weather resistance, yellowing resistance and the like. When used as an aqueous base paint, a part of the remaining carboxylic acid such as dibasic acid is left and partially neutralized with a base such as an amine or ammonia to obtain a water-soluble or water-dispersible material. It can be a resin.

  Examples of polyether polyols include, for example, hydroxides (lithium, sodium, potassium, etc.), strong basic catalysts (alcoholates, alkylamines, etc.), composite metal cyanide complexes (metals) Porphyrin, zinc hexacyanocobaltate complex, etc.) or the like, by random or block addition of an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, etc.) or a mixture thereof to a polyhydroxy compound. And polyether polyols obtained; polyether polyols obtained by reacting polyamine compounds (such as ethylenediamines) with alkylene oxides; and acrylics using these polyether polyols as a medium. Obtained by polymerizing bromide or the like, so-called polymer polyols, and the like.

  Examples of the polyvalent hydroxy compound include (i) diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like, (ii) e.g. erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, Sugar alcohol compounds such as mannitol, galactitol, and rhamnitol; (iii) monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodeose; and (iv) trehalose, for example. Disaccharides such as sucrose, maltose, cellobiose, gentiobiose, lactose and melibiose; (v) trisaccharides such as raffinose, gentianose and meletitose; i) For example, tetrasaccharides such as stachyose, and the like.

  The acrylic polyol can be obtained, for example, by copolymerizing a polymerizable monomer having one or more active hydrogens in one molecule and another monomer copolymerizable with the polymerizable monomer.

  The acrylic polyol is, for example, an acrylate having active hydrogen (such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, or 2-hydroxybutyl acrylate), or a methacrylate having active hydrogen. (Such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate), and glycerin and trimethylolpropane. (Meth) acrylic acid esters having polyvalent active hydrogen such as triol (meth) acrylic acid monoester; polyether polyols (polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) and the above active hydrogen Monoether with (meth) acrylic acid ester; adduct of glycidyl (meth) acrylate with monobasic acid such as acetic acid, propionic acid, p-tert-butylbenzoic acid; having the above active hydrogen (meth) One or more selected from the group consisting of adducts obtained by ring-opening polymerization of lactones (ε-caprolactam, γ-valerolactone, etc.) with the active hydrogen of acrylates as essential components, if necessary. (Meth) acrylates (methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacrylic acid-n -Butyl, isobutyl methacrylate, n-hexyl methacrylate, methacrylic acid Cyclohexyl acid, lauryl methacrylate, glycidyl methacrylate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.), unsaturated amides (acrylamide, N-methylol acrylamide, diacetone acrylamide, etc.), Or vinyl monomers having a hydrolyzable silyl group (vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ- (meth) acrylopropyltrimethoxysilane, etc.), and other polymerizable monomers (styrene, vinyltoluene, vinyl acetate, One or more selected from the group consisting of acrylonitrile, dibutyl fumarate and the like can be obtained by copolymerization in a conventional manner.

  For example, an acrylic polyol is obtained by performing solution polymerization of the above monomer component in the presence of a radical polymerization initiator such as a known peroxide or an azo compound, and diluting with an organic solvent or the like as necessary. Can be. When the aqueous base acrylic polyol is obtained, it can be produced by a known method such as a method of polymerizing a solution of an olefinically unsaturated compound and converting it into an aqueous layer or an emulsion polymerization. In this case, water solubility or water dispersibility can be imparted by neutralizing an acidic portion such as a carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or a sulfonic acid-containing monomer with an amine or ammonia.

  The fluorine polyol is a polyol containing fluorine in the molecule, for example, a fluoroolefin, a cyclovinyl ether, a hydroxyalkyl vinyl ether disclosed in JP-A-57-34107, JP-A-61-215311 and the like. Copolymers such as vinyl monocarboxylate and the like can be mentioned.

  The hydroxyl value of the polyol is not particularly limited, but is preferably from 10 mgKOH / g to 200 mgKOH / g. Among them, the lower limit is more preferably 20 mgKOH / g, and particularly preferably 30 mgKOH / g. The acid value of the polyol is preferably from 0 mgKOH / g to 30 mgKOH / g. The hydroxyl value and the acid value can be measured according to JIS K1557.

  Among the above, as the polyol, an acrylic polyol is preferable from the viewpoint of weather resistance, chemical resistance, and hardness, and a polyester polyol is preferable from the viewpoint of mechanical strength and oil resistance.

The equivalent ratio (NCO / OH ratio) of the isocyanate group of the polyisocyanate composition of the present invention to the hydroxyl group of the compound having two or more active hydrogens in the molecule is preferably 0.2 or more and 5.0 or less. It is more preferably from 0.4 to 3.0, and particularly preferably from 0.5 to 2.0. When the equivalent ratio is equal to or more than the above lower limit, a tougher coating film can be obtained. When the equivalent ratio is equal to or less than the upper limit, the smoothness of the coating film can be further improved.
If necessary, a melamine-based curing agent such as a complete alkyl type, a methylol type alkyl, or an imino group type alkyl can be added to the coating composition.

  The compound having two or more active hydrogens in the molecule, the polyisocyanate composition and the coating composition of the present invention can be used as a mixture with an organic solvent. It is preferable that the organic solvent does not have a functional group that reacts with a hydroxyl group and an isocyanate group. Further, it is preferable that the compound is compatible with the polyisocyanate composition. Such organic solvents include ester compounds, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether-based compounds, polyethylene glycol dicarboxylate-based compounds, and hydrocarbon solvents generally used as paint solvents. And aromatic solvents.

  The compound having two or more active hydrogens in the molecule, the polyisocyanate composition and the coating composition of the present invention may be any of catalysts and pigments according to the purpose and use within a range that does not impair the effects of the present invention. Various additives used in the art, such as a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a surfactant, and a hydrophilic agent for the surface of a coating film, may be used in combination. .

  Examples of catalysts for promoting curing include metal salts such as dibutyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, and cobalt salts; triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N- Tertiary amines such as dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N, N'-endoethylenepiperazine, N, N'-dimethylpiperazine and the like.

  As an example of the coating film surface hydrophilic agent, a silicate compound is preferable. For example, a compound represented by the following formula (XX), that is, at least one kind of silicate compound selected from tetraalkoxysilane, a condensate of tetraalkoxysilane, and a derivative of tetraalkoxysilane is exemplified. By containing a silicate compound, when a coating film is produced in combination with the base polyol, the coating film surface is made hydrophilic and rain streak stain resistance is exhibited.

[In the general formula (XX), a plurality of R ⁸¹ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group. A plurality of R ⁸¹ may be the same or different. ]

[ ^R81 ]

R ⁸¹ is each independently an alkyl group having 1 to 10 carbon atoms or an aryl group. The alkyl group having 1 to 10 carbon atoms in R ⁸¹ may be linear or branched, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methyl Pentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl Group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, a Examples include a sooctyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group.
Examples of the aryl group for R ⁸¹ include, for example, a phenylene group, a pentalenylene group, an indenylene group, a naphthylene group, an anthracenylene group, a heptalenylene group, an octalenylene group, an azulenylene group, and the like. Examples include those in which at least two hydrogen atoms have been substituted with a halogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms substituting hydrogen atoms include the above exemplified as the alkyl group having 1 to 10 carbon atoms in R ^51.

<Coating>
The coating composition using the polyisocyanate composition of the present invention as a curing agent can be used as a coating such as roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating and the like. For example, it is useful as a primer or top coat for materials such as metals (steel plates, surface-treated steel plates, etc.), plastics, woods, films, and inorganic materials. It is also useful as a paint for imparting aesthetics, weather resistance, acid resistance, rust resistance, chipping resistance, etc. to pre-coated metal including rust-proof steel plates, automotive coatings and the like. It is also useful as a urethane raw material for adhesives, pressure-sensitive adhesives, elastomers, foams, surface treatment agents and the like.

<Water dispersion>

The aqueous dispersion of the present invention is an aqueous dispersion containing the polyisocyanate composition, the blocked polyisocyanate composition, or the hydrophilic polyisocyanate composition of the present invention, and water.
Since the polyisocyanate composition, the blocked polyisocyanate composition, or the hydrophilic polyisocyanate composition of the present invention has high water dispersibility, it can be easily dispersed in water.
The aqueous dispersion of the present invention may contain a solvent other than water. The solvent other than the water can contain up to 20% by mass. Examples of the solvent in this case are not particularly limited, for example, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl Ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol mono Met Ether acetate, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4 -Butanediol, 1,3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit and the like. These solvents may be used alone or in combination of two or more. From the viewpoint of dispersibility in water, the solvent is preferably one having a solubility in water of 5% by mass or more, and specifically, dipropylene glycol dimethyl ether and dipropylene glycol monomethyl ether are preferred.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to specific examples and comparative examples.However, the embodiments of the present invention are not limited by the following examples and comparative examples unless they exceed the gist thereof. It is not something to be done.

The physical properties of the polyisocyanate composition in Examples (1-1) -1 to (1-1) -28 and Comparative Examples (1-1) -1 to (1-1) -10 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<Viscosity>

The viscosity was measured at 25 ° C. using an E-type viscometer (manufactured by Tokimec). In the measurement, a standard rotor (1 ° 34 ′ × R24) was used. The rotation speed is as follows.
100rpm (less than 128mPa · s)
50 rpm (128 mPa · s to 256 mPa · s)
20 rpm (in the case of 256 mPa · s to 640 mPa · s)
10 rpm (for 640 mPa · s to 1280 mPa · s)
5 rpm (for 1280 mPa · s to 2560 mPa · s)

<NCO content>

The NCO content (% by mass) was determined by back titration with 1N hydrochloric acid after neutralizing the isocyanate group in the measurement sample with an excess of 2N amine.

<Calculated NCO content>

The NCO content of the polyisocyanate composition used in the synthesis of the blocked polyisocyanate composition is determined by the above method, and the NCO content mass is determined from the charged polyisocyanate composition [A].
The calculated NCO content was determined by the following equation.
Calculated NCO content (% by mass) = 100 × [A] / total charged mass

<Conversion rate>

The conversion was defined as the area ratio of the peak having a number average molecular weight larger than that of the unreacted triisocyanate, based on the number average molecular weight based on polystyrene by GPC measurement using the following apparatus.
Apparatus: "HLC-8120GPC" (trade name) manufactured by Tosoh Corporation
Column: Tosoh “TSKgel SuperH1000” (trade name) x 1
"TSKgel SuperH2000" (product name) x 1
"TSKgel SuperH3000" (trade name) x 1 Carrier: tetrahydrofuran Detection method: differential refractometer Sample concentration: 5 wt / vol%,
Outflow rate: 0.6 mL / min,
Column temperature: 30 ° C.

<Method for determining molar ratio of iminooxadiazinedione structure to isocyanurate structure>
Using Bruker (Bruker) Co. Biospin AVANCE 600 (trade ^name), 13 to measure the C-NMR, it was determined iminooxadiazinedione structure, and the molar ratio of isocyanurate structures.

Specific measurement conditions were as follows.
¹³ C-NMR apparatus: AVANCE600 (manufactured by Bruker)
Cryoprobe (Bruker)
Cryo Probe
CPDUL
600S3-C / HD-05Z
Resonant frequency: 150MHz
Concentration: 60 wt / vol%
Shift standard: CDCl ₃ (77 ppm)
Number of integration: 10000 times Pulse program: zgpg30 (proton complete decoupling method, waiting time 2 sec)

The integral value of the following signal was divided by the number of measured carbons, and each molar ratio was determined from the value.
Iminooxadiazinedione structure: around 144.5 ppm: integral value ÷ 1
Isocyanurate structure: around 148.5 ppm: integral value ÷ 3
Next, the molar ratio of the iminooxadiazinedione structure to the isocyanurate structure was determined from the obtained iminooxadiazinedione structure and the molar ratio of the isocyanurate structure.

<Degree of viscosity reduction of polyisocyanate composition (1)>

From the result of the viscosity measurement of the polyisocyanate mixture, a case where the viscosity was less than 1000 mPa · s / 25 ° C. was evaluated as “○”, and a case where the viscosity was 1000 mPa · s / 25 ° C. or higher was evaluated as “x”.

<Method for evaluating dryness of polyisocyanate composition (1)>

An acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the polyisocyanate compositions were blended at an equivalent ratio of isocyanate group / hydroxyl group of 1.0. And butyl acetate to adjust the solid content to 50% by mass. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 23 ° C./50% RH. After a lapse of a specific time, a cotton ball (a cylindrical shape having a diameter of 2.5 cm and a height of 2.0 cm) was placed on the coating film, and a weight of 100 g was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the trace of cotton remaining on the coating film was observed. ◎ when the time when the mark disappeared completely was within 8 hours, Δ when it was more than 8 hours and less than 9 hours, △ when it was more than 9 hours and less than 10 hours, and 場合 when it was more than 10 hours Is indicated by x.

<Low viscosity degree of block polyisocyanate composition (1)>

From the results of the viscosity measurement of the blocked polyisocyanate composition, the case where the viscosity was less than 1000 mPa · s / 25 ° C. was evaluated as “○”, and the case where the viscosity was 1000 mPa · s / 25 ° C. or higher was evaluated as “X”.

<Method for evaluating dryness of blocked polyisocyanate composition (1)>

Acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the blocked polyisocyanate compositions are mixed at an isocyanate group / hydroxyl equivalent ratio of 1.0. Then, the solid content was adjusted to 50% by mass with butyl acetate. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 100 ° C. for 30 minutes. A cotton ball (a cylindrical shape having a diameter of 2.5 cm and a height of 2.0 cm) was placed on the coating film, and a 100 g weight was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the trace of cotton remaining on the coating film was observed. The case where the trace was completely invisible was rated as 跡, the case where the trace was slightly visible was rated as △, and the case where a clear trace was seen was rated as x.

<Method for Evaluating Opacity of Underlayer of (Block) Polyisocyanate Composition>

Acrylic (registered trademark) A-801-P (resin content: 50%, hydroxyl value: 50.0 mgKOH / g resin) manufactured by DIC, which is an acrylic polyol, and has the same composition as in Examples and Comparative Examples (block ) Each of the polyisocyanate compositions was blended at an isocyanate group / hydroxyl group equivalent ratio of 1.0 and adjusted to 50% solids with butyl acetate. Thereafter, the resin solid content was adjusted to 50% by adding or subtracting a solvent to a cationic electrodeposition coated plate (black) manufactured by Standard Test Piece Co., Ltd., and applied by an applicator so as to have a resin film thickness of 40 μm. After the application, it was allowed to stand at room temperature for 30 minutes, and then left in an oven at 140 ° C. for 30 minutes. Then, after cooling and confirming that the coating film reached 23 ° C., the arithmetic average roughness Ra value was measured using the following apparatus under the following conditions. The smaller the Ra value is, the better the background concealing property is.
Measuring device: Scanning white interference microscope manufactured by Zygo, brand name "NewView600s" Magnification: 2.5 times Measurement method: Ra value is measured (arithmetic deviation from center line)
When the Ra value is 0.025 μm or less, it is judged that the background opacity is good, and the result is indicated by ◎. When the Ra value is more than 0.025 μm and 0.04 μm or less, it is judged that the background opacity is almost good. When it was more than 0.04 μm, it was judged that the undercoat opacity was poor, and was indicated by X.

<Method of evaluating adhesion of (block) polyisocyanate composition to base coat>

A mild steel plate was coated with acrylic polyol (resin solid content concentration 55%, hydroxyl value 30 mg KOH / g resin) so that the resin film thickness became 40 micrometers. After leaving at room temperature for 30 minutes, a (block) polyisocyanate having the same composition as the acrylic polyol (product name of Nuplex Resin, Setalux 1903, resin solids concentration 75%, hydroxyl value 150 mgKOH / resin g), Examples and Comparative Examples Each of the compositions was blended in an isocyanate group / hydroxyl group equivalent ratio of 1.0, and butyl acetate was used to adjust the paint viscosity of Ford Cup No. 5 4 and the coating composition was adjusted to 20 seconds. The obtained coating composition was applied so as to have a resin film thickness of 30 micrometers. After being left at room temperature for 15 minutes, it was cured in an oven at 140 ° C. for 30 minutes. The adhesion test of this coating film was performed according to JIS K5600-5-6. No release coating is shown as 、, release coating is more than 0% and 25% or less, 、, release coating is more than 25% and 50% or less Δ, and release coating is more than 50% as ×. Was.

<Low viscosity degree of hydrophilic polyisocyanate composition (1)>

From the result of the viscosity measurement of the hydrophilic polyisocyanate composition, a case where the viscosity was less than 1000 mPa · s / 25 ° C. was evaluated as “○”, and a case where the viscosity was 1000 mPa · s / 25 ° C. or higher was evaluated as “x”.

<Method for evaluating dryness of hydrophilic polyisocyanate composition>

An acrylic dispersion (trade name “SETAQUA6510” of Nuplex Resin, resin concentration 42%, hydroxyl group concentration 4.2% (based on resin)) and an equivalent ratio of isocyanate group / hydroxyl group of each of the hydrophilic polyisocyanate compositions of 1 And adjusted with water to a solid content of 40% by mass. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 23 ° C./50% RH. After a lapse of a specific time, a cotton ball (a cylindrical shape having a diameter of 2.5 cm and a height of 2.0 cm) was placed on the coating film, and a weight of 100 g was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the trace of cotton remaining on the coating film was observed. The case where the time when the trace was completely invisible was within 9 hours, ◎, the case where it was more than 9 hours and within 10 hours, and the case where it was more than 10 hours was x.

<Method for Evaluating Opacity of Underlayer of Hydrophilic Polyisocyanate Composition>

Hydrophilic polyisocyanate composition having an acrylic dispersion (trade name “SETAQUA6510” of Nuplex Resin Co., resin concentration 42%, hydroxyl group concentration 4.2% (based on resin)), and the same composition as in Examples and Comparative Examples Were mixed at an equivalent ratio of isocyanate group / hydroxyl group of 1.0, and adjusted to a solid content of 40% with ion-exchanged water. Thereafter, the resin solid content was adjusted to 50% by adding or subtracting a solvent to a cationic electrodeposition coated plate (black) manufactured by Standard Test Piece Co., Ltd., and applied by an applicator so as to have a resin film thickness of 40 μm. After the application, it was allowed to stand at room temperature for 30 minutes, and then allowed to stand in an oven at 120 ° C. for 30 minutes. Then, after cooling and confirming that the coating film reached 23 ° C., the arithmetic average roughness Ra value was measured using the following apparatus under the following conditions. The smaller the Ra value is, the better the background concealing property is.
Measuring device: Scanning white interference microscope manufactured by Zygo, brand name "NewView600s" Magnification: 2.5 times Measurement method: Ra value is measured (arithmetic deviation from center line)
When the Ra value is 0.025 μm or less, it is judged that the background opacity is good, and the result is indicated by ◎. When the Ra value is more than 0.025 μm and 0.04 μm or less, it is judged that the background opacity is almost good. When it was more than 0.04 μm, it was judged that the undercoat opacity was poor, and was indicated by X.

<Method of evaluating adhesion of hydrophilic polyisocyanate composition to base coat>

A mild steel plate was coated with acrylic polyol (resin solid content concentration 55%, hydroxyl value 30 mg KOH / resin g) so as to have a resin film thickness of 40 micrometers. After standing at room temperature for 30 minutes, it has the same composition as the acrylic dispersion (42% resin concentration, 4.2% hydroxyl group concentration (based on resin), trade name of "SETAQUA6510" manufactured by Nuplex Resin) (resin standard) (Examples and Comparative Examples). Block) with each of the polyisocyanate compositions at an equivalent ratio of isocyanate groups / hydroxyl groups of 1.0, and the viscosity of the paint in Ford Cup No. 1 with ion-exchanged water. 4 and the coating composition was adjusted to 40 seconds. The obtained coating composition was applied so as to have a resin film thickness of 30 micrometers. After being left at room temperature for 15 minutes, it was cured in an oven at 140 ° C. for 30 minutes. The adhesion test of this coating film was performed according to JIS K5600-5-6. No release coating is shown as 、, release coating is more than 0% and 25% or less, 、, release coating is more than 25% and 50% or less Δ, and release coating is more than 50% as ×. Was.

<Storage stability evaluation method>

300 g of the polyisocyanate composition was placed in a 500 mL container, replaced with nitrogen, and stored at 23 ° C. for 300 days.
When the change in the number average molecular weight (after storage / before storage) was less than 1.5, it was judged that the storage stability was good.

[Synthesis Example (1-1) -1]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, 1,060 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter sometimes referred to as "triamine") was added to 1500 g of methanol. The solution was dissolved, and 1800 mL of 35% concentrated hydrochloric acid was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. The obtained triamine hydrochloride (650 g) was suspended as fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / Hr. Then, the temperature was further increased and maintained at 180 ° C., and phosgene was continuously blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, the residue was distilled under vacuum to obtain a colorless and transparent 4-isocyanatomethyl-1,8-octanemethylene diisocyanate having a boiling point of 161 to 163 ° C./1.2 mmHg (hereinafter referred to as “NTI”). ) Was obtained.) 420 g was obtained. Its NCO content was 50.0% by weight.

[Synthesis Example (1-1) -2]
Synthesis of LTI

122.2 g of ethanolamine, 100 mL of o-dichlorobenzene, and 420 mL of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube, and ice-cooled hydrogen chloride gas was introduced. Converted to salt. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C. to dissolve ethanolamine hydrochloride, and hydrogen chloride gas was introduced to obtain lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 to 30 mL / min, and the reaction solution was heated to 116 ° C. and maintained at this temperature until no more water distilled. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 mL of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 120 ° C., phosgene was added at a rate of 0.4 mol / hour. Blowing was started at a constant speed and maintained for 10 hours, and then the temperature was raised to 150 ° C. The suspension almost dissolved. After cooling and filtration, the dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation to obtain 80.4 g of a colorless and transparent LTI having a boiling point of 155 to 157 ° C / 0.022 mmHg. Its NCO content was 47.1% by weight.

[Example (1-1) -1]
Synthesis of P (1-1) -1

The inside of the four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was set to a nitrogen atmosphere, 50 g of NTI was charged as a monomer, and the temperature was maintained at 60 ° C. for 2 hours. Thereafter, 5 mg of a catalyst tetramethylammonium fluoride tetrahydrate containing 95% by mass of n-butanol was added, and the reaction was carried out. When the conversion reached 41%, dibutylphosphoric acid was added to stop the reaction. P (1-1) -1 was obtained. The viscosity of the obtained polyisocyanate P (1-1) -1 was 39 mPa · s / 25 ° C., the NCO content was 42.8% by mass, and the molar ratio of the iminooxadiazinedione structure to the isocyanurate structure was 0. .25.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-1) -1 was ○, the evaluation result of dryness was ○, the evaluation result of base opacity was ◎, and the evaluation result of adhesion to the base coating film was ◎. Was. These results are shown in Table (1-1) -1.

[Examples (1-1) -2 to (1-1) -8, Comparative examples (1-1) -1 to (1-1) -2]
Synthesis of P (1-1) -2 to P (1-1) -8, P (1-1) -10, P (1-1) -11

The procedure was performed in the same manner as in Example (1-1) -1 except that the monomer, the catalyst, the catalyst diluting solvent (concentration), and the conversion were as shown in Table (1-1) -1. In addition, the viscosity of the obtained polyisocyanate composition, the NCO content, the molar ratio of the iminooxadiazinedione structure to the isocyanurate structure, the degree of low viscosity, the drying property evaluation result, the base opacity evaluation result, and the base coating film Are shown in Table (1-1) -1.

[Example (1-1) -9]
Synthesis of P (1-1) -9

Example (1-1) -1 except that the monomer, the catalyst, the catalyst diluting solvent (concentration), and the conversion were as shown in Table (1-1) -1, and the amount of the catalyst was changed to 10 mg. Was performed in the same manner as described above.
In addition, the viscosity of the obtained polyisocyanate composition, the NCO content, the molar ratio of the iminooxadiazinedione structure to the isocyanurate structure, the degree of low viscosity, the drying property evaluation result, the base opacity evaluation result, and the base coating film Are shown in Table (1-1) -1.

[Comparative Example (1-1) -3]
Synthesis of P (1-1) -12

The reaction solution obtained in Comparative Example (1-1) -2 was fed to a thin film evaporator to remove unreacted HDI, thereby obtaining a polyisocyanate composition P (1-1) -12. The viscosity of the obtained polyisocyanate composition P (1-1) -12 is 2300 mPa · s / 25 ° C., the NCO content is 21.5% by mass, and the molar ratio of iminooxadiazinedione structure to isocyanurate structure Was 0.03.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-1) -12 was ×, the evaluation result of dryness was ○, the evaluation result of base opacity was ×, and the evaluation result of adhesion to the base coating film was ○. Was. These results are shown in Table (1-1) -1.

[Comparative Example (1-1) -4]

The NTI monomer synthesized in Synthesis Example (1-1) -1 was used alone. The degree of viscosity reduction of NTI was 低, the result of evaluation of dryness was ○, the result of evaluation of opacity of the underlayer was ◎, and the result of evaluation of adhesion to the undercoat film was ×. These results are shown in Table (1-1) -1.

In the above Table (1-1) -1, the catalyst and catalyst diluent described in abbreviations respectively mean the following materials.
C (1-1) -1: tetramethylammonium fluoride tetrahydrate C (1-1) -2: tetrabutylphosphonium hydrogen difluoride C (1-1) -3: tetramethylammonium capryate C (1- 1) -4: benzyltrimethylammonium hydroxide PMA: propylene glycol monomethyl ether acetate

[Example (1-1) -10]
Synthesis of blocked polyisocyanate composition

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-1) obtained in Example (1-1) -1 was obtained. 20 g of -1 and 16.4 g of butyl acetate were charged, and the temperature was heated to 70 ° C. Thereafter, 20.2 g of 3,5-dimethylpyrazole was added with stirring, the temperature was maintained at 70 ° C, and the mixture was stirred for 1 hour. , NCO content became 0.0%, and a blocked polyisocyanate composition was obtained. The viscosity of the obtained blocked polyisocyanate composition was 195 mPa · s / 25 ° C., and the calculated NCO content was 15.1% by mass.
Further, the degree of viscosity reduction of the obtained blocked polyisocyanate composition was ○, the evaluation result of drying property was ○, the evaluation result of opacity of the undercoat was ○, and the evaluation result of adhesion to the undercoat film was ◎. These results are shown in Table (1-1) -2.

[Examples (1-1) -11 to (1-1) -17, Comparative Examples (1-1) -5 to (1-1) -7]
Synthesis of blocked polyisocyanate composition

Same as Example (1-1) -10, except that 3,5-dimethylpyrazole addition amount, butyl acetate addition amount, and type of polyisocyanate composition were as described in Table (1-1) -2. Carried out. Table (1-1) shows the viscosity of the obtained blocked polyisocyanate composition, the calculated NCO content, the degree of reduction in viscosity, the evaluation result of drying property, the evaluation result of base opacity, and the evaluation result of adhesion to the base coating film. -2.

[Example (1-1) -18]
Synthesis of hydrophilic polyisocyanate composition

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube, a nitrogen atmosphere was introduced, and 20 g of the polyisocyanate composition P (1-1) -1 obtained in Example 41 was obtained. 8.6 g of polyethylene oxide (manufactured by Nippon Emulsifier Co., Ltd., trade name: “MPG-130” number average molecular weight = 420) was charged and kept at 100 ° C. for 4 hours while heating and stirring to obtain a hydrophilic polyisocyanate. The viscosity of the obtained hydrophilic polyisocyanate composition was 49 mPa · s / 25 ° C., and the NCO content was 26.9% by mass.
Further, the degree of viscosity reduction was ○, the result of evaluation of dryness was ○, the result of evaluation of opacity of the underlayer was ◎, and the result of evaluation of adhesion to the undercoat film was ◎.

[Examples (1-1) -19 to (1-1) -25, Comparative Examples (1-1) -8 to (1-1) -10)]
Synthesis of hydrophilic polyisocyanate composition

It carried out like Example (1-1) -18 except having added the amount of MPG-130 and the kind of polyisocyanate composition as described in Table (1-1) -3. In addition, the viscosity, NCO content, degree of viscosity reduction, dryness evaluation result, base opacity evaluation result, and adhesion evaluation result to the base coating film of the obtained hydrophilic polyisocyanate composition are shown in Table (1-1). -3.

[Example (1-1) -26]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-1) -1 obtained in Example (1-1) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, the evaluation result of dryness was ○, the evaluation result of base opacity was ◎, the evaluation result of adhesion to the base coating film was ◎, and the storage stability evaluation result was good. .

[Example (1-1) -27]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-1) -1 obtained in Example (1-1) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, the evaluation result of dryness was ○, the evaluation result of base opacity was ◎, the evaluation result of adhesion to the base coating film was ◎, and the storage stability evaluation result was good. .

[Synthesis Example (1-1) -3]
Synthesis of D (1-1) -1

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was set to a nitrogen atmosphere, 20 g of NTI was charged, heated to 60 ° C., 7.7 g of methanol was added, and stirring was continued. After holding for a time, an N-substituted carbamic acid ester D (1-1) -1 was obtained.

[Example (1-1) -28]

0.03 g of N-substituted carbamic acid ester D (1-1) -1 was added to 300 g of the polyisocyanate composition P (1-1) -1 obtained in Example (1-1) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, the evaluation result of dryness was ○, the evaluation result of base opacity was ◎, the evaluation result of adhesion to the base coating film was ◎, and the storage stability evaluation result was good. .

  As described above, the polyisocyanate composition, the blocked polyisocyanate composition, or the hydrophilic polyisocyanate composition of each Example has a low viscosity, and has excellent drying properties, concealing properties for the base, and adhesion to the base coating film. It was confirmed that it was excellent.

The physical properties of the polyisocyanate composition in Examples (1-1) -29 to (1-1) -43 and Comparative Examples (1-1) -11 to (1-1) -18 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<Viscosity>
As described above.

<NCO content>

As described above.

<Calculated NCO content>
As described above.

<Theoretical reaction rate>

The theoretical conversion is expressed as a conversion assuming that all multimers are trimers. The theoretical reaction rate c (%) is calculated based on the NCO% (x%) of the synthesized polyisocyanate composition, the NCO% (a%) of the used triisocyanate (see the following formula [B]), and the triisocyanate trimer. From NCO% (b%) (see the following formula [C]), it can be obtained by the following formula [D].
NCO% of used triisocyanate: (a) = (molecular weight of NCO / molecular weight of used triisocyanate) × 100 (%) [B]
NCO% of triisocyanate trimer: (b) = (molecular weight of NCO / molecular weight of triisocyanate trimer) × 100 (%) [C]
Theoretical reaction rate c (%) = [(xa) / (ba)] x 100 (%) [D]

<Low viscosity of polyisocyanate composition (2)>

From the viscosity measurement results of the polyisocyanate mixture, the case where the temperature is 100 mPa · s / 25 ° C. or less is Δ, the case where the temperature is more than 100 mPa · s / 25 ° C. and 1000 mPa · s / 25 ° C. or less, and the case where the temperature is more than 1000 mPa · s / 25 ° C. X.

<Low viscosity (2) of blocked polyisocyanate composition>

From the viscosity measurement results of the blocked polyisocyanate composition, the case where 400 mPa · s / 25 ° C. or less is Δ, the case where it is 400 mPa · s / 25 ° C. or more and less than 1000 mPa · s / 25 ° C., or 1000 mPa · s / 25 ° C. or more The case was evaluated as x.

<Low viscosity (2) of hydrophilic polyisocyanate composition>

From the viscosity measurement results of the hydrophilic polyisocyanate composition, the case where the viscosity is less than 100 mPa · s / 25 ° C is Δ, the case where the viscosity is 100 mPa · s / 25 ° C or more and less than 1000 mPa · s / 25 ° C, or 1000 mPa · s / 25 ° C or more. Was evaluated as x.

<Method for evaluating water dispersibility of hydrophilic polyisocyanate composition>

Acrylic dispersion (trade name “SETAQUA6510” manufactured by Nuplex Resin Co., Ltd., resin content concentration 42%, hydroxyl group concentration 4.2% (based on resin)) and polyisocyanate composition were each treated with an equivalent ratio of isocyanate group / hydroxyl group of 1.0. And prepared with water to have a solid content of 40% by mass. When the above-mentioned coating composition was prepared, a substance to which no gel-like substance was attached at all upon stirring was rated as ○, a substance with slight adhesion was rated as Δ, and a substance with large adhesion was rated as x.

<Compatibility evaluation method with polar polyol>

Asahi Kasei Corporation's Duranol (registered trademark) T-5652, which is a polycarbonate diol, and each of the polyisocyanate compositions are blended at an equivalent ratio of isocyanate group / hydroxyl group of 1.0 so that butyl acetate has a solid content of 50% by mass. Was prepared. After coating the prepared coating composition on a glass plate so as to have a dry film thickness of 40 μm, the coating composition was cured at 80 ° C. for 30 minutes, and the haze value of the coating film was measured with the following equipment.
Apparatus: Direct reading haze computer "HGM-2DP" (trade name) manufactured by Suga Test Instruments Co., Ltd.
Standard plate: 2 mm thick glass plate, haze value of less than 0.1 is ◎, 0.1 to less than 0.5 is 、, 0.5 to less than 1.0 is Δ1, And 0.0 or more was evaluated as x.

<Crack resistance of coating film (wet heat repetition test)>

Equivalent ratio of isocyanate group / hydroxyl group to each of an acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin concentration 70%, hydroxyl value 138.6 mgKOH / g) and polyisocyanate composition or block polyisocyanate composition 1.0 and prepared with butyl acetate to a solid content of 50% by mass. The prepared coating composition was blended on a clear coating film (Nplex Resin's trade name "SETALUX1753" and Asahi Kasei Corporation HDI-based polyisocyanate "TKA-100" in an isocyanate group / hydroxyl group equivalent ratio of 1.0, A clear coating film obtained by preparing a coating composition having a solid content of 50% by mass with butyl acetate, applying the prepared coating composition to an aluminum plate so as to have a dry film thickness of 50 μm, and curing at 100 ° C. for 60 minutes. ) Was applied to a dry film thickness of 40 μm, and then cured at 100 ° C. for 30 minutes. In the obtained coating film sample, “60 ° C./90% RH / 6 hours → 60 ° C./30% RH / 6 hours → 10 ° C./90% RH / 6 hours → 10 ° C./30% RH / 6 hours” A cycle test (60 cycles) was performed with one cycle, and the state of the coating film after the cycle test was observed. What occurred was marked as x.

<Storage stability evaluation method>

As described above.

[Synthesis Example (1-1) -4]
Synthesis of LTI

122.2 g of ethanolamine, 100 mL of o-dichlorobenzene, and 420 mL of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube, and ice-cooled hydrogen chloride gas was introduced. Converted to salt. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C. to dissolve ethanolamine hydrochloride, and hydrogen chloride gas was introduced to obtain lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 to 30 mL / min, and the reaction solution was heated to 116 ° C. and maintained at this temperature until no more water distilled. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 mL of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 120 ° C., phosgene was added at a rate of 0.4 mol / hour. Blowing was started at a constant speed and maintained for 10 hours, and then the temperature was raised to 150 ° C. The suspension almost dissolved. After cooling and filtration, the dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation to obtain 80.4 g of a colorless and transparent LTI having a boiling point of 155 to 157 ° C / 0.022 mmHg. Its NCO content was 47.1% by weight.

[Synthesis Example (1-1) -5]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, 1,060 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter sometimes referred to as "triamine") was added to 1500 g of methanol. The solution was dissolved, and 1800 mL of 35% concentrated hydrochloric acid was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. The obtained triamine hydrochloride (650 g) was suspended as fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / Hr. Then, the temperature was further increased and maintained at 180 ° C., and phosgene was continuously blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, the residue was distilled under vacuum to obtain a colorless and transparent 4-isocyanatomethyl-1,8-octanemethylene diisocyanate having a boiling point of 161 to 163 ° C./1.2 mmHg (hereinafter referred to as “NTI”). ) Was obtained.) 420 g was obtained. Its NCO content was 50.0% by weight.

[Example (1-1) -29]
Synthesis of P (1-1) -13

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, charged with 50 g of NTI as a monomer, and kept at 80 ° C. for 2 hours. Thereafter, a solution prepared by dissolving 10 mg of benzyltrimethylammonium capric acid in 50 mg of isobutanol, which is a catalyst for isocyanuration, was added, and an isocyanuration reaction was carried out. When the NCO% became 47.7%, a 25% NTI solution of dibutylphosphoric acid was used. Was added to terminate the reaction. The reaction liquid was further kept at 120 ° C. for 15 minutes to obtain a polyisocyanate composition P (1-1) -13. The viscosity of the polyisocyanate composition P (1-1) -13 was 13 mPa · s / 25 ° C., and the theoretical conversion was 15.0%.
Furthermore, Table (1-1) -4 shows the results of the evaluation of the degree of viscosity reduction of the polyisocyanate composition P (1-1) -13, the compatibility with the polar polyol, and the evaluation of the crack resistance of the coating film.

[Examples (1-1) -30 to (1-1) -36, Comparative Examples (1-1) -11 to (1-1) -14]
Synthesis of P (1-1) -13 to P (1-1) -24

The procedure was performed in the same manner as in Example (1-1) -29, except that the monomer, the catalyst, the terminator, the reaction temperature, and the NCO% at the time of stopping the reaction were as described in Table (1-1) -4. . In addition, Table (1-1) -4 shows the viscosity, theoretical reaction rate, degree of viscosity reduction, evaluation of compatibility with polar polyol, and evaluation of crack resistance of the coating film of the obtained polyisocyanate composition. .

In the above Table (1-1) -4, the catalyst and the terminator described in the abbreviations respectively mean the following materials.
BTMA-H: benzyltrimethylammonium hydroxide.
BTMA-A: benzyltrimethylammonium capric acid.
TMA-A: tetramethylammonium capric acid.
DBP: dibutyl phosphoric acid.
D2EHP: di (2-ethylhexyl) phosphoric acid.

[Example (1-1) -37]
Synthesis of blocked polyisocyanate composition

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-1) obtained in Example (1-1) -33 was obtained. -20 g of -17 and 16.4 g of butyl acetate were charged, and the temperature was heated to 70 ° C. Thereafter, 20.2 g of 3,5-dimethylpyrazole was added with stirring, the temperature was maintained at 70 ° C, and the mixture was stirred for 1 hour. , NCO content became 0.0%, and a blocked polyisocyanate composition was obtained. The viscosity of the obtained blocked polyisocyanate composition was 290 mPa · s / 25 ° C., and the calculated NCO content was 15.2% by mass.
Furthermore, Table (1-1) -5 shows the degree of viscosity reduction of the obtained blocked polyisocyanate composition, the compatibility with polar polyols, and the results of evaluating the crack resistance of the coating film.

[Example (1-1) -38, Comparative example (1-1) -15, (1-1) -16]
Synthesis of blocked polyisocyanate composition

Example (1-1) -37 except that the amount of 3,5-dimethylpyrazole added, the amount of butyl acetate added, and the type of the polyisocyanate composition used were as described in Table (1-1) -5. The same was done. Table (1-1) -5 shows the viscosity of the obtained blocked polyisocyanate composition, the calculated NCO content, the degree of viscosity reduction, the compatibility with polar polyols, and the evaluation results of the crack resistance of the coating film. did.

[Example (1-1) -39]
Synthesis of hydrophilic polyisocyanate composition

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and 20 g of the polyisocyanate composition P (1-1) -9 obtained in Example 41 was obtained. 8.6 g of polyethylene oxide as a compound (manufactured by Nippon Emulsifier Co., Ltd., trade name “MPG-130” number average molecular weight = 420) was charged, and kept at 100 ° C. with stirring for 4 hours to obtain a hydrophilic polyisocyanate. . The viscosity of the obtained hydrophilic polyisocyanate composition was 49 mPa · s / 25 ° C., and the NCO content was 26.9% by mass.
Further, the degree of viscosity reduction was ○, the result of evaluation of dryness was ○, the result of evaluation of opacity of the underlayer was ◎, and the result of evaluation of adhesion to the undercoat film was ◎.

[Example (1-1) -40, Comparative example (1-1) -17, (1-1) -18]
Synthesis of hydrophilic polyisocyanate composition

It carried out like Example (1-1) -39 except having added MPG-130 and the kind of polyisocyanate composition to be used as described in Table (1-1) -6. The results of evaluation of the viscosity, degree of viscosity reduction, and water dispersibility of the obtained hydrophilic polyisocyanate composition are shown in Table (1-1) -6.

[Example (1-1) -41]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-1) -13 obtained in Example (1-1) -29.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -29, and the storage stability evaluation result was good.

[Example (1-1) -42]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-1) -13 obtained in Example (1-1) -29.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -29, and the storage stability evaluation result was good.

[Synthesis Example (1-1) -6]
Synthesis of C (1-1) -5

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was set to a nitrogen atmosphere, 20 g of NTI was charged, heated to 60 ° C., 7.7 g of methanol was added, and stirring was continued. After holding for a while, an N-substituted carbamic acid ester C (1-1) -5 was obtained.

[Example (1-1) -43]

0.03 g of N-substituted carbamic acid ester C (1-1) -5 was added to 300 g of the polyisocyanate composition P (1-1) -13 obtained in Example (1-1) -29.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -29, and the storage stability evaluation result was good.

  As described above, the polyisocyanate composition, the blocked polyisocyanate composition, or the hydrophilic polyisocyanate composition of each of the examples to which the present invention is applied has a low viscosity, and is compatible with a polar polyol, and has an excellent coating resistance. It was confirmed that it had excellent cracking properties and water dispersibility.

The physical properties of the polyisocyanate composition in Examples (1-1) -44 to (1-1) -58 and Comparative Examples (1-1) -19 to (1-1) -26 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<Viscosity> As described above.

<NCO content>
As described above.

<Calculated NCO content>
As described above.

<Theoretical reaction rate>
As described above.

<Method for evaluating dryness of polyisocyanate composition (2)>

Acrylic polyol (trade name "SETALUX1753" of Nuplex Resin, resin concentration: 70%, hydroxyl value: 138.6 mgKOH / g) and each of the polyisocyanate compositions are mixed at an isocyanate group / hydroxyl equivalent ratio of 1.0. Then, the solid content was adjusted to 40% by mass with butyl acetate. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 23 ° C./50% RH. After a lapse of a specific time, a cotton ball (a cylindrical shape having a diameter of 2.5 cm and a height of 2.0 cm) was placed on the coating film, and a weight of 100 g was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the trace of cotton remaining on the coating film was observed. ◎ when the time when the mark disappeared completely was within 7 hours, Δ when it was more than 7 hours to 8 hours, Δ when it was more than 8 hours to less than 10 hours, and more than 10 hours. When there was, it was evaluated as x.

<Hardness evaluation of polyisocyanate composition coating film>

Acrylic polyol (trade name "SETALUX1753" of Nuplex Resin, resin concentration: 70%, hydroxyl value: 138.6 mgKOH / g) and each of the polyisocyanate compositions are mixed at an isocyanate group / hydroxyl equivalent ratio of 1.0. Then, the solid content was adjusted to 40% by mass with butyl acetate. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 23 ° C./50% RH for 15 minutes and 120 ° C./1 hour.
The coating film hardness of the cured coating film was measured using a pencil hardness tester (load: 500 g, pencil hardness = HB, pencil accuracy: 45 degrees), and relative evaluation was performed. Check for scratches or thick marks, ◎ for no scratches, ○ for slight streaks, ○ Was reached as x.

<Evaluation of hardness of coated film of blocked polyisocyanate composition>

An acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin content concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the blocked polyisocyanate compositions were converted to an isocyanate group / hydroxyl equivalent ratio of 1.0. It was blended and adjusted to a solid content of 40% by mass with butyl acetate. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 150 ° C. for 30 minutes.
The coating film hardness of the cured coating film was measured using a pencil hardness tester (load: 500 g, pencil hardness = HB, pencil accuracy: 45 degrees), and relative evaluation was performed. Check for scratches or thick marks, ◎ for no scratches, ○ for slight streaks, ○ Was reached as x.

<Method for evaluating dryness of hydrophilic polyisocyanate composition>

As described above.

<Evaluation of water resistance of polyisocyanate composition coating film>

An acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin content concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the blocked polyisocyanate compositions were converted to an isocyanate group / hydroxyl equivalent ratio of 1.0. It was blended and adjusted to a solid content of 40% by mass with butyl acetate. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 150 ° C. for 30 minutes. The cured coating film was immersed in water and left at room temperature for 3 days, and the state of the coating film was visually observed. X: If any coating abnormality such as whitening or blistering of the coating film (stripping between the glass plate and the coating film) is observed on the entire surface, the coating film is partially or slightly abnormal. The case was marked with △, and the case where none was seen was marked with ○.

<Storage stability evaluation method>

As described above.

[Synthesis Example (1-1) -7]
Synthesis of LTI

122.2 g of ethanolamine, 100 mL of o-dichlorobenzene, and 420 mL of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube, and ice-cooled hydrogen chloride gas was introduced. Converted to salt. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C. to dissolve ethanolamine hydrochloride, and hydrogen chloride gas was introduced to obtain lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 to 30 mL / min, and the reaction solution was heated to 116 ° C. and maintained at this temperature until no more water distilled. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 mL of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 120 ° C., phosgene was added at a rate of 0.4 mol / hour. Blowing was started at a constant speed and maintained for 10 hours, and then the temperature was raised to 150 ° C. The suspension almost dissolved. After cooling and filtration, the dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation to obtain 80.4 g of a colorless and transparent LTI having a boiling point of 155 to 157 ° C / 0.022 mmHg. Its NCO content was 47.1% by weight.

[Synthesis Example (1-1) -8]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, 1,060 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter sometimes referred to as "triamine") was added to 1500 g of methanol. The solution was dissolved, and 1800 mL of 35% concentrated hydrochloric acid was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. The obtained triamine hydrochloride (650 g) was suspended as fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / Hr. Then, the temperature was further increased and maintained at 180 ° C., and phosgene was continuously blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, the residue was distilled under vacuum to obtain a colorless and transparent 4-isocyanatomethyl-1,8-octanemethylene diisocyanate having a boiling point of 161 to 163 ° C./1.2 mmHg (hereinafter referred to as “NTI”). ) Was obtained.) 420 g was obtained. Its NCO content was 50.0% by weight.

[Example (1-1) -44]

Synthesis of P (1-1) -21 A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was set to a nitrogen atmosphere, charged with 50 g of NTI as a monomer, and charged at 80 ° C. for 2 hours. Held. Thereafter, a solution prepared by dissolving 10 mg of benzyltrimethylammonium capric acid in 50 mg of isobutanol, which is a catalyst for isocyanuration, was added, and an isocyanuration reaction was carried out. When the NCO% became 47.7%, a 25% NTI solution of dibutylphosphoric acid was used. Was added to terminate the reaction. The reaction liquid was further kept at 120 ° C. for 15 minutes to obtain a polyisocyanate composition P (1-1) -25. The theoretical conversion of the polyisocyanate composition P (1-1) -25 was 22.3% by mass.
Further, Table (1-1) -7 shows the results of evaluation of the polyisocyanate composition P (1-1) -25, drying property, and hardness and water resistance of the coating film.

[Examples (1-1) -45 to (1-1) -51, Comparative Examples (1-1) -19 to (1-1) -22]
Synthesis of P (1-1) -26 to P (1-1) -37

The procedure was performed in the same manner as in Example (1-1) -44, except that the monomer, the catalyst, the terminator, the reaction temperature, and the NCO% at the time of stopping the reaction were as described in Table (1-1) -7. . Table (1-1) -7 shows the theoretical reactivity of the obtained polyisocyanate composition for evaluation of the drying property, the hardness of the coating film, and the water resistance evaluation result.

In the above Table (1-1) -7, the catalyst and the terminator described in the abbreviations respectively mean the following materials.
BTMA-H: benzyltrimethylammonium hydroxide.
BTMA-A: benzyltrimethylammonium capric acid.
TMA-A: tetramethylammonium capric acid.
DBP: dibutyl phosphoric acid.
D2EHP: di (2-ethylhexyl) phosphoric acid.

[Example (1-1) -52]

Synthesis of Blocked Polyisocyanate Composition A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing pipe was set to a nitrogen atmosphere, and the polyisocyanate composition obtained in Example (1-1) -48 was obtained. 30 g of product P (1-1) -30 and 25 g of butyl acetate were charged, and the temperature was heated to 70 ° C. Thereafter, 15 g of 3,5-dimethylpyrazole was added with stirring, and the temperature was maintained at 70 ° C for 1 hour. As a result of stirring, the NCO content became 0.0%, and a blocked polyisocyanate composition was obtained. The calculated NCO content of the obtained blocked polyisocyanate composition was 9.1% by mass.
Furthermore, the obtained block polyisocyanate composition, hardness of the coating film, and the results of water resistance evaluation are shown in Table (1-1) -8.

[Example (1-1) -53, Comparative examples (1-1) -23, (1-1) -24]
Synthesis of blocked polyisocyanate composition

Examples (1-1) -52 and 3,5-dimethylpyrazole addition amount, butyl acetate addition amount, and the type of polyisocyanate composition used were as described in Table (1-1) -8. The same was done. In addition, Table (1-1) -8 shows the hardness and water resistance evaluation results of the coating film of the obtained blocked polyisocyanate composition.

[Example (1-1) -54]

Synthesis of hydrophilic polyisocyanate composition A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate obtained in Example (1-1) -48. 30 g of the composition P (1-1) -30 and 9.6 g of a hydrophilic compound, polyethylene oxide (manufactured by Nippon Emulsifier Co., Ltd., trade name "MPG-130", number average molecular weight = 420) were charged and heated to 100 ° C. The mixture was kept for 4 hours while stirring to obtain a hydrophilic polyisocyanate. Regarding the viscosity of the obtained hydrophilic polyisocyanate composition, the NCO content was 12.9% by mass.
Table (1-1) -9 shows the evaluation results of the drying property, the hardness of the coating film, and the water resistance of the obtained polyisocyanate composition.

[Example (1-1) -55, Comparative examples (1-1) -25, (1-1) -26]
Synthesis of hydrophilic polyisocyanate composition

It carried out like Example (1-1) -54 except having added the amount of MPG-130 and the kind of polyisocyanate composition to be used as described in Table (1-1) -9. In addition, Table (1-1) -9 shows the evaluation results of the dryness, the hardness of the coating film, and the water resistance of the obtained hydrophilic polyisocyanate composition.

[Example (1-1) -56]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-1) -26 obtained in Example (1-1) -44.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -30, and the storage stability evaluation result was good.

[Example (1-1) -57]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-1) -26 obtained in Example (1-1) -44.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -44, and the storage stability evaluation result was good.

[Synthesis Example (1-1) -9]
Synthesis of C (1-1) -6

The inside of the four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was set to a nitrogen atmosphere, charged with 20 g of NTI, heated to 60 ° C., added with 7.7 g of methanol, and stirred for 4 hours. Retained to give N-substituted carbamic acid ester C (1-1) -6.

[Example (1-1) -58]

0.03 g of N-substituted carbamic acid ester C (1-1) -6 was added to 300 g of the polyisocyanate composition P (1-1) -26 obtained in Example (1-1) -44.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -44, and the storage stability evaluation result was good.

  From the above, it was confirmed that the polyisocyanate composition, the blocked polyisocyanate composition, or the hydrophilic polyisocyanate composition of each Example to which the present invention was applied was excellent in drying property, hardness of a coating film, and water resistance. .

Physical properties of the polyisocyanate composition in Examples (1-1) -59 to (1-1) -68 and Comparative Examples (1-1) -27 to (1-1) -29 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<NCO content>
As described above.

<Conversion rate, polyisocyanate compound ratio, trimer ratio>

The conversion was defined as the area ratio of the peak having a number average molecular weight larger than that of the unreacted triisocyanate, based on the number average molecular weight based on polystyrene by GPC measurement using the following apparatus. The polyisocyanate ratio was determined as the area ratio of the peak having a number average molecular weight larger than that of triisocyanate, based on the number average molecular weight based on polystyrene by GPC measurement using the following apparatus. If not removed, the conversion will be the polyisocyanate ratio).
The trimer ratio was defined as an area ratio of a polyisocyanate peak corresponding to a triisocyanate trimer, based on a polystyrene-based number average molecular weight measured by GPC using the following apparatus.
Equipment: "HLC-8320GPC" (trade name) manufactured by Tosoh Corporation
Column: Tosoh “TSKgel SuperH1000” (trade name) x 1
"TSKgel SuperH2000" (product name) x 1
"TSKgel SuperH3000" (trade name) x 1 Carrier: tetrahydrofuran Detection method: differential refractometer Sample concentration: 5 wt / vol%
Outflow rate: 0.6 mL / min
Column temperature: 30 ° C.
Analysis software: Tosoh Corporation, EcoSEC-WS Version1.06
(Analysis conditions)
Detection sensitivity: 3.0mV / min
Base judgment value: 0.1 mV / min
Excluded area: 10mV × sec
Excluded height: 0mV
Exclusion half width: 0 sec

<Method for evaluating dryness of polyisocyanate composition (2)>

As described above.

<Method of evaluating adhesion of polyisocyanate composition to base coat>

Acrylic polyol (resin solid content concentration: 55%, hydroxyl value: 30 mg KOH / resin g) was coated on a mild steel plate so as to have a resin film thickness of 40 micrometers, left at room temperature for 30 minutes, and then acrylic polyol (a product name of Nuplex Resin, Setalux 1903, resin solids concentration 75%, hydroxyl value 150 mg KOH / resin g) and each of the (block) polyisocyanate compositions are blended at an isocyanate group / hydroxyl equivalent ratio of 1.0, and the paint viscosity is reduced with butyl acetate to a Ford cup. No. The coating composition adjusted to 20 seconds at 4 was applied so as to have a resin film thickness of 30 micrometers. After being left at room temperature for 15 minutes, it was cured in an oven at 140 ° C. for 30 minutes.
The obtained coating film sample was subjected to a cycle test (30 cycles) with one cycle of “60 ° C./90%/12 hours ℃ 10 ° C./25%/12 hours”, and the adhesion of the coating film after the cycle test The test was performed according to JIS K5600-5-6.無 し indicates that there was no release coating, ○ indicates that less than half of the release coating was present, and X indicates that half or more of the release coatings were present.

<Storage stability evaluation method>

As described above.

[Synthesis Example (1-1) -10]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, 1530 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter referred to as triamine) was dissolved in 2250 g of methanol, and 35% concentrated hydrochloric acid was added thereto. 2700 ml was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. 975 g of the obtained triamine hydrochloride was suspended as fine powder in 7500 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was introduced at a rate of 300 g / Hr. The temperature was further raised to 180 ° C., and phosgene was blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, vacuum distillation is performed to obtain colorless and transparent 4-isocyanatomethyl-1,8-octamethylene diisocyanate having a boiling point of 161 to 163 ° C./1.2 mmHg (hereinafter “NTI”). 630 g, which had an NCO content of 50.0% by weight.

[Example (1-1) -59]
Synthesis of P (1-1) -38

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, 500 g of NTI and 0.5 g of isobutanol were charged as monomers, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 50 mg of benzyltrimethylammonium hydroxide, an isocyanurate-forming catalyst, was added, and an isocyanurate-forming reaction was performed. When the yield became 3%, dibutyl phosphoric acid was added, and the reaction solution was kept at 120 ° C. for 15 minutes to carry out the reaction. Stopped. When the reaction was stopped, the NCO content of the reaction solution was 48.8%. Unreacted NTI was removed from the reaction solution obtained by the thin film distillation apparatus to obtain polyisocyanate P (1-1) -38. Physical properties (NCO content, functionality, polyisocyanate ratio, trimer ratio) of the obtained polyisocyanate P (1-1) -38, evaluation results of dryness of the polyisocyanate composition, and adhesion to the undercoat film The results of the sex evaluation are shown in Table (1-1) -10.

[Examples (1-1) -60 to (1-1) -65]

It carried out like Example (1-1) -59 except having set the monomer, the initiator, the terminator, and the conversion of Table (1-1) -10 as described. In addition, the physical properties (NCO content, functionality, polyisocyanate ratio, trimer ratio) of the obtained polyisocyanate composition, the results of evaluating the dryness of the polyisocyanate composition, and the results of evaluating the adhesion to the undercoat film are described. The results are shown in Table (1-1) -10.

[Comparative Example (1-1) -27]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, 500 g of NTI and 0.5 g of isobutanol were charged as monomers, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 50 mg of benzyltrimethylammonium hydroxide, an isocyanurate-forming catalyst, was added, and an isocyanurate-forming reaction was performed. When the yield reached 38.5%, dibutyl phosphoric acid was added, and the reaction solution was kept at 120 ° C. for 15 minutes. The reaction was stopped to obtain polyisocyanate P (1-1) -45. The NCO content of polyisocyanate P (1-1) -45 was 48.8%. Physical properties (NCO content, functionality, polyisocyanate ratio, trimer ratio) of the obtained polyisocyanate P (1-1) -45, the dryness evaluation result of the polyisocyanate composition, and adhesion to the undercoat film The results of the sex evaluation are shown in Table (1-1) -10.

[Comparative Example (1-1) -27]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, 500 g of HDI and 0.5 g of isobutanol were charged as monomers, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 50 mg of benzyltrimethylammonium hydroxide, an isocyanuration catalyst, was added, and an isocyanuration reaction was performed. When the yield reached 40.0%, dibutyl phosphoric acid was added, and the reaction solution was kept at 120 ° C. for 15 minutes. The reaction was stopped to obtain polyisocyanate P (1-1) -46. The NCO content of polyisocyanate P (1-1) -46 was 42.4%. Physical properties (NCO content, functionality, polyisocyanate ratio, trimer ratio) of the obtained polyisocyanate P (1-1) -46, evaluation results of dryness of the polyisocyanate composition, and adhesion to the undercoat film The results of the sex evaluation are shown in Table (1-1) -10.

[Comparative Example (1-1) -29]

The reaction solution obtained in Comparative Example (1-1) -28 was fed to a thin film evaporator to remove unreacted HDI, to obtain a polyisocyanate composition P (1-1) -47. The NCO content of the obtained polyisocyanate composition P (1-1) -47 was 23.0% by mass.
Furthermore, the physical properties (NCO content, functionality, polyisocyanate ratio, trimer ratio) of the polyisocyanate composition P (1-1) -47, the dryness evaluation results of the polyisocyanate composition, and the The results of the adhesion evaluation are shown in Table (1-1) -10.

In Table (1-1) -10, each material described in abbreviations means the following materials.
・ BTMA-H: benzyltrimethylammonium hydroxide ・ BTMA-A: benzyltrimethylammonium capric acid ・ TMA-A: tetramethylammonium capric acid ・ DBP: dibutylphosphoric acid

[Example (1-1) -66]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-1) -38 obtained in Example (1-1) -59.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -59, and the storage stability evaluation result was good.

[Example (1-1) -67]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-1) -38 obtained in Example (1-1) -59.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -59, and the storage stability evaluation result was good.

[Synthesis Example (1-1) -11]

The inside of the four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was set to a nitrogen atmosphere, charged with 20 g of NTI, heated to 60 ° C., added with 7.7 g of methanol, and stirred for 4 hours. Retained to give N-substituted carbamic acid ester C (1-1) -7.

[Example (1-1) -68]

0.03 g of N-substituted carbamic acid ester C (1-1) -7 was added to 300 g of the polyisocyanate composition P (1-1) -38 obtained in Example (1-1) -59.
Each evaluation result of this polyisocyanate composition was the same as that of Example (1-1) -59, and the storage stability evaluation result was good.

The physical properties of the polyisocyanate composition in Examples (1-2) -1 to (1-2) -21 and Comparative examples (1-2) -1 to (1-2) -15 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<Viscosity>

As described above.

<NCO content>

As described above.

<Calculated NCO content>

As described above.

<Conversion rate>

As described above.

<Method of measuring molar ratio between isocyanurate structure and allophanate structure>

The isocyanurate structure and the allophanate structure in the polyisocyanate composition were determined by the following method.
The molar ratio of the isocyanurate structure and the allophanate structure was determined by ¹³ C-NMR measurement using a Biospin Avance 600 (trade name) manufactured by Bruker as an instrument. The peak position of each functional group and structure is shown for NTI. However, since the peak position is changed by triisocyanate, calibration was performed using a standard substance or the like as appropriate.
Specific measurement conditions were as follows.
¹³ C-NMR apparatus: AVANCE600 (manufactured by Bruker)
Cryoprobe (Bruker)
Cryo Probe
CPDUL
600S3-C / HD-05Z
Resonant frequency: 150MHz
Concentration: 60 wt / vol%
Shift standard: CDCl ₃ (77 ppm)
Number of integration: 10000 times Pulse program: zgpg30 (proton complete decoupling method, waiting time 2 sec)

The integral value of the following signal was divided by the number of measured carbons, and each molar ratio was determined from the value.
Isocyanurate structure: around 148.6 ppm: integral value ÷ 3
Allophanate structure: around 154 ppm: integrated value ÷ 1
Next, the molar ratio between the isocyanurate structure and the allophanate structure was determined from the obtained molar ratio between the isocyanurate structure and the allophanate structure.

<Low viscosity of polyisocyanate composition (3)>

From the viscosity measurement results of the polyisocyanate mixture, the case where the temperature is 250 mPa · s / 25 ° C. or less is Δ, the case where the temperature is more than 250 mPa · s / 25 ° C. and 2000 mPa · s / 25 ° C. or less, and the case where the temperature is more than 2000 mPa · s / 25 ° C. X.

<Method for evaluating silicate compatibility of polyisocyanate composition>

After mixing 5 g of the polyisocyanate composition, 1 g of the silicate compound “MKC silicate MS58B30” (trade name, condensate of butyl-modified methyl silicate, manufactured by Mitsubishi Chemical Corporation) and 4 g of butyl acetate, thoroughly mix the mixture at 23 ° C. It was left still for 2 hours under the environment. After standing, it was evaluated as ○ if clear, △ if slightly turbid, and × if turbid or precipitated.

<Method for evaluating dryness of polyisocyanate composition (1)>

As described above.

<Method for evaluating recoat adhesion of coating film using coating composition using polyisocyanate composition>
Acrylic polyol (resin solids concentration 55%, hydroxyl value 30 mg KOH / resin g) and a polyisocyanate composition are mixed with mild steel plate so that the equivalent ratio of hydroxyl group to isocyanate group becomes 1: 1 and then coated with butyl acetate. The viscosity is Ford Cup No. The coating composition was prepared in such a manner as to be 20 seconds at 4. Next, the prepared coating composition was applied so as to have a resin film thickness of 30 micrometers. Further, it was left for 72 hours at 23 ° C. and 50% humidity. The adhesion test of this coating film was performed according to JIS K5600-5-6.無 し indicates no peeling coating film, ○ indicates partial floating in the cut portion, Δ indicates half or less peeling, and × indicates half or more peeling coating.

<Evaluation method for abrasion resistance test of coating film by coating composition using polyisocyanate composition>
Acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the polyisocyanate compositions are blended at an isocyanate group / hydroxyl equivalent ratio of 1.0. Then, a coating composition was prepared with butyl acetate so as to have a solid content of 50% by mass. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 100 ° C. for 30 minutes to obtain a coating film. The abrasion resistance test was performed on the obtained coating film using a rubbing tester (manufactured by Taihei Rika Kogyo Co., Ltd.) by the following method.

The 20 ° gloss of the coated surface was measured in advance. A cleanser (trade name: Marzen Cleanser, manufactured by Maruzen Cleanser Co., Ltd.) and water were mixed at a ratio of 3: 2 to obtain an abrasive. About 1 g of the abrasive was adhered to a sponge of a rubbing tester, and a load of 200 g was applied thereto to rub the coating film of the test plate back and forth 20 times.
Thereafter, the coated surface was washed with running water and air-dried, and then the coated surface was measured for 20 ° gloss. The 20 ° gloss retention is calculated by the following equation, and the value is used as the evaluation value of the scratch resistance.
20 ° gloss retention = (20 ° gloss after test / 20 ° gloss before test) × 100
If the 20 ° gloss retention was 90% or more, it was rated as ◎, from less than 90% to 80% or more, ○, from less than 80% to 50% or more, and で あ れ ば if less than 50%.

<Low viscosity degree of block polyisocyanate composition (1)>

As described above.

<Evaluation method for abrasion resistance test of coating film by coating composition using blocked polyisocyanate composition>

Acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin concentration: 70%, hydroxyl value: 138.6 mgKOH / g) and each of the blocked polyisocyanate compositions were obtained at an isocyanate group / hydroxyl equivalent ratio of 1.0. The coating composition was prepared by mixing and mixing with butyl acetate to a solid content of 50% by mass. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 140 ° C. for 30 minutes to obtain a coating film. The abrasion resistance test was performed on the obtained coating film using a rubbing tester (manufactured by Taihei Rika Kogyo Co., Ltd.) by the following method.
The 20 ° gloss of the coated surface was measured in advance. A cleanser (trade name: Marzen Cleanser, manufactured by Maruzen Cleanser Co., Ltd.) and water were mixed at a ratio of 3: 2 to obtain an abrasive. About 1 g of the abrasive was adhered to a sponge of a rubbing tester, and a load of 200 g was applied thereto to rub the coating film of the test plate back and forth 20 times.
Thereafter, the coated surface was washed with running water and air-dried, and then the coated surface was measured for 20 ° gloss. The 20 ° gloss retention is calculated by the following equation, and the value is used as the evaluation value of the scratch resistance.
20 ° gloss retention = (20 ° gloss after test / 20 ° gloss before test) × 100
If the 20 ° gloss retention was 90% or more, it was rated as ◎, from less than 90% to 80% or more, ○, from less than 80% to 50% or more, and で あ れ ば if less than 50%.

<Evaluation method for abrasion resistance test of coating film using coating composition using hydrophilic polyisocyanate composition>

An acrylic polyol (trade name “SETALUX1753” manufactured by Nuplex Resin, resin content concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the hydrophilic polyisocyanate compositions were mixed at an isocyanate group / hydroxyl equivalent ratio of 1.0. And a coating composition was prepared by adjusting the solid content to 50% by mass with butyl acetate. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 100 ° C. for 30 minutes to obtain a coating film. The abrasion resistance test was performed on the obtained coating film using a rubbing tester (manufactured by Taihei Rika Kogyo Co., Ltd.) by the following method.
The 20 ° gloss of the coated surface was measured in advance. A cleanser (trade name: Marzen Cleanser, manufactured by Maruzen Cleanser Co., Ltd.) and water were mixed at a ratio of 3: 2 to obtain an abrasive. About 1 g of the abrasive was adhered to a sponge of a rubbing tester, and a load of 200 g was applied thereto to rub the coating film of the test plate back and forth 20 times.
Thereafter, the coated surface was washed with running water and air-dried, and then the coated surface was measured for 20 ° gloss. The 20 ° gloss retention is calculated by the following equation, and the value is used as the evaluation value of the scratch resistance.
20 ° gloss retention = (20 ° gloss after test / 20 ° gloss before test) × 100
If the 20 ° gloss retention was 90% or more, it was rated as ◎, from less than 90% to 80% or more, ○, from less than 80% to 50% or more, and で あ れ ば if less than 50%.

<Storage stability evaluation method>

As described above.

[Synthesis Example (1-2) -1]
Synthesis of LTI

122.2 g of ethanolamine, 100 mL of o-dichlorobenzene, and 420 mL of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube, and ice-cooled hydrogen chloride gas was introduced. Converted to salt. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C. to dissolve ethanolamine hydrochloride, and hydrogen chloride gas was introduced to obtain lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 to 30 mL / min, and the reaction solution was heated to 116 ° C. and maintained at this temperature until no more water distilled. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 mL of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 120 ° C., phosgene was added at a rate of 0.4 mol / hour. Blowing was started at a constant speed and maintained for 10 hours, and then the temperature was raised to 150 ° C. The suspension almost dissolved. After cooling and filtration, the dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation to obtain 80.4 g of a colorless and transparent LTI having a boiling point of 155 to 157 ° C / 0.022 mmHg. Its NCO content was 47.1% by weight.

[Synthesis Example (1-2) -2]
Synthesis of GTI

275 g of glutamate hydrochloride, 800 g of ethanolamine hydrochloride, and 150 ml of toluene are placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. The mixture was heated at reflux at 24 ° C. for 24 hours. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 270 g of bis (2-aminoethyl) glutamate trihydrochloride. 85 g of this bis (2-aminoethyl) glutamate trihydrochloride was suspended in 680 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 135 ° C., phosgene was added at a rate of 0.8 mol / hour. The reaction product was filtered, concentrated under reduced pressure, and purified by a thin-film evaporator to obtain 54 g of GTI. The NCO content was 39.8% by weight.

[Synthesis Example (1-2) -3]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, 1,060 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter sometimes referred to as "triamine") was added to 1500 g of methanol. The solution was dissolved, and 1800 mL of 35% concentrated hydrochloric acid was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. The obtained triamine hydrochloride (650 g) was suspended as fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / Hr. Then, the temperature was further increased and maintained at 180 ° C., and phosgene was continuously blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, the residue was distilled under vacuum to obtain a colorless and transparent 4-isocyanatomethyl-1,8-octanemethylene diisocyanate having a boiling point of 161 to 163 ° C./1.2 mmHg (hereinafter referred to as “NTI”). ) Was obtained.) 420 g was obtained. Its NCO content was 50.0% by weight.

[Example (1-2) -1]
Synthesis of P (1-2) -1

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, 100 g of NTI and 0.2 g of methanol were charged as monomers, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 0.01 g of benzyltrimethylammonium hydroxide, an isocyanurate-forming catalyst, was added, and an isocyanurate-forming reaction was performed. When the conversion reached 50%, dibutylphosphoric acid was added to stop the reaction. The reaction liquid was further kept at 120 ° C. for 15 minutes to obtain a polyisocyanate composition P (1-2) -1. The viscosity of the polyisocyanate composition P (1-2) -1 was 110 mPa · s / 25 ° C., and the NCO content was 41.0% by mass.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-2) -1 was ○, the silicate compatibility was △, the drying property was ○, the recoat adhesion was ◎, and the scratch resistance was ○. These results are shown in Table (1-2) -1.

[Examples (1-2) -2 to (1-2) -6, Comparative Examples (1-2) -1 to (1-2) -5)
Synthesis of P (1-2) -2 to P (1-2) -6, S (1-2) -1 to S (1-2) -5

It carried out similarly to Example (1-2) -1 except having set the monomer, the catalyst, the terminator, the reaction temperature, and the conversion as described in Table (1-2) -1. In addition, Table (1-2) -1 shows the evaluation results of the viscosity, NCO content, degree of viscosity reduction, silicate compatibility, drying property, recoat adhesion, and abrasion resistance of the obtained polyisocyanate composition. Described.

In the above Table (1-2) -1, the catalyst and the terminator described in the abbreviations respectively mean the following materials.
BTMA-H: benzyltrimethylammonium hydroxide.
BTMA-A: benzyltrimethylammonium capric acid.
TMA-A: tetramethylammonium capric acid.
DBP: dibutyl phosphoric acid.
DOP: di (2-ethylhexyl) phosphoric acid.

[Example (1-2) -7]
Synthesis of Block Polyisocyanate Composition P (1-2) -7

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and 20 g of the polyisocyanate composition P (1-2) -1 and 17.0 g of butyl acetate were charged. The temperature was heated to 70 ° C., and then 19.7 g of 3,5-dimethylpyrazole was added with stirring, the temperature was maintained at 70 ° C., and the mixture was stirred for 1 hour. A composition was obtained. The viscosity of the obtained blocked polyisocyanate composition was 520 mPa · s / 25 ° C., and the calculated NCO content was 14.5% by mass. Further, the degree of viscosity reduction of the obtained blocked polyisocyanate composition was ○, and the scratch resistance was △. These results are shown in Table (1-2) -2.

[Examples (1-2) -8 to (1-2) -12, Comparative Examples (1-2) -6 to (1-2) -10]
Synthesis of P (1-2) -8 to P (1-2) -12, S (1-2) -6 to S (1-2) -10

Example (1-2) -7, except that 3,5-dimethylpyrazole addition amount, butyl acetate addition amount, and type of polyisocyanate composition used were as described in Table (1-2) -2. The same was done. In addition, Table (1-2) -2 shows the evaluation results of the viscosity, the calculated NCO content, the degree of viscosity reduction, and the scratch resistance of the obtained blocked polyisocyanate composition.

(Example (1-2) -13) Synthesis of hydrophilic polyisocyanate composition (P (1-2) -13)

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-2) obtained in Example (1-2) -4 was obtained. -4 g (20 g) and 8.2 g of a hydrophilic compound polyethylene oxide (manufactured by Nippon Emulsifier Co., Ltd., trade name "MPG-130" number average molecular weight = 420), and the mixture was heated and stirred at 100 ° C. for 4 hours. A hydrophilic polyisocyanate was obtained. The viscosity of the obtained hydrophilic polyisocyanate composition was 240 mPa · s / 25 ° C., and the NCO content was 26.2% by mass.
Further, the degree of viscosity reduction was ○, and the scratch resistance was △.

[Examples (1-2) -14 to (1-2) -18, Comparative Examples (1-2) -11 to (1-2) -15]
Synthesis of P (1-2) -14 to P (1-2) -18, S (1-2) -11 to S (1-2) -15

The procedure was performed in the same manner as in Example (1-2) -13, except that the amount of MPG-130 added and the type of the polyisocyanate composition used were as described in Table (1-2) -3. The results of evaluation of the viscosity, NCO content, degree of viscosity reduction, and scratch resistance of the obtained hydrophilic polyisocyanate composition are shown in Table (1-2) -3.

[Example (1-2) -19]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-2) -1 obtained in Example (1-2) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, silicate compatibility was △, drying was ○, recoat adhesion was ◎, abrasion resistance was ○, and storage stability evaluation results were good.

[Example (1-2) -20]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-2) -1 obtained in Example (1-2) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, silicate compatibility was △, drying was ○, recoat adhesion was ◎, abrasion resistance was ○, and storage stability evaluation results were good.

[Synthesis Example (1-2) -4]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was set to a nitrogen atmosphere, 20 g of NTI was charged, heated to 60 ° C., 7.7 g of methanol was added, and stirring was continued. After holding for a time, an N-substituted carbamic acid ester C (1-2) -1 was obtained.

[Example (1-2) -21]

0.03 g of N-substituted carbamic acid ester C (1-2) -1 was added to 300 g of the polyisocyanate composition P (1-2) -1 obtained in Example (1-2) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, silicate compatibility was △, drying was ○, recoat adhesion was ◎, abrasion resistance was ○, and storage stability evaluation results were good.

  As described above, the polyisocyanate compositions of the respective examples to which the present invention was applied had low viscosity and excellent silicate compatibility, and the coating compositions using the polyisocyanate compositions of the present invention exhibited drying properties and recoat adhesion. Excellent in nature. Further, a coating film produced using the above-mentioned coating composition has good scratch resistance. Furthermore, it was confirmed that the blocked polyisocyanate composition or the hydrophilic polyisocyanate composition produced from the polyisocyanate composition of the present invention had low viscosity and imparted good scratch resistance to the coating film.

The physical properties of the polyisocyanate composition in Examples (1-3) -1 to (1-3) -16 and Comparative Examples (1-3) -1 to (1-3) -6 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<Viscosity>

As described above.

<NCO content>

As described above.

<Calculated NCO content>

As described above.

<Conversion rate>

As described above.

<Method for determining molar ratio of uretdione structure to isocyanurate structure>
Using Bruker (Bruker) Co. Biospin AVANCE 600 (trade ^name), was measured 13 C-NMR, it was determined molar ratio of uretdione structures, and isocyanurate structures.

Specific measurement conditions were as follows.
¹³ C-NMR apparatus: AVANCE600 (manufactured by Bruker)
Cryoprobe (Bruker)
Cryo Probe
CPDUL
600S3-C / HD-05Z
Resonant frequency: 150MHz
Concentration: 60 wt / vol%
Shift standard: CDCl ₃ (77 ppm)
Number of integration: 10000 times Pulse program: zgpg30 (proton complete decoupling method, waiting time 2 sec)

The integral value of the following signal was divided by the number of measured carbons, and each molar ratio was determined from the value.
Uretdione structure: around 157.3 ppm: integral value ÷ 2
Isocyanurate structure: around 148.5 ppm: integral value ÷ 3
Next, the molar ratio of the uretdione structure to the isocyanurate structure was determined from the obtained uretdione structure and the molar ratio of the isocyanurate structure.

<Degree of viscosity reduction of polyisocyanate composition (1)>

As described above.

<Method for evaluating dryness of polyisocyanate composition (1)>

As described above.

<Low viscosity degree of block polyisocyanate composition (1)>

As described above.

<Method for evaluating dryness of blocked polyisocyanate composition (2)>

Acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the blocked polyisocyanate compositions are mixed at an isocyanate group / hydroxyl equivalent ratio of 1.0. Then, the solid content was adjusted to 50% by mass with butyl acetate. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 120 ° C. for 30 minutes. A cotton ball (a cylindrical shape having a diameter of 2.5 cm and a height of 2.0 cm) was placed on the coating film, and a 100 g weight was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the trace of cotton remaining on the coating film was observed. The case where no trace was seen was evaluated as ○, and the case where a trace was seen was evaluated as ×.

<Method of evaluating adhesion of (block) polyisocyanate composition to base coat>

As described above.

<Low viscosity degree of hydrophilic polyisocyanate composition (1)>

As described above.

<Method for evaluating dryness of hydrophilic polyisocyanate composition>

As described above.

<Method of evaluating adhesion of hydrophilic polyisocyanate composition to base coat>

As described above.

<Storage stability evaluation method>

As described above.

[Synthesis Example (1-3) -1]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, 1,060 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter sometimes referred to as "triamine") was added to 1500 g of methanol. The solution was dissolved, and 1800 mL of 35% concentrated hydrochloric acid was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. The obtained triamine hydrochloride (650 g) was suspended as fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / Hr. Then, the temperature was further increased and maintained at 180 ° C., and phosgene was continuously blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, the residue was distilled under vacuum to obtain a colorless and transparent 4-isocyanatomethyl-1,8-octanemethylene diisocyanate having a boiling point of 161 to 163 ° C./1.2 mmHg (hereinafter referred to as “NTI”). ) Was obtained.) 420 g was obtained. Its NCO content was 50.0% by weight.

[Synthesis Example (1-3) -2]
Synthesis of LTI

122.2 g of ethanolamine, 100 mL of o-dichlorobenzene, and 420 mL of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube, and ice-cooled hydrogen chloride gas was introduced. Converted to salt. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C. to dissolve ethanolamine hydrochloride, and hydrogen chloride gas was introduced to obtain lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 to 30 mL / min, and the reaction solution was heated to 116 ° C. and maintained at this temperature until no more water distilled. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 mL of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 120 ° C., phosgene was added at a rate of 0.4 mol / hour. Blowing was started at a constant speed and maintained for 10 hours, and then the temperature was raised to 150 ° C. The suspension almost dissolved. After cooling and filtration, the dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation to obtain 80.4 g of a colorless and transparent LTI having a boiling point of 155 to 157 ° C / 0.022 mmHg. Its NCO content was 47.1% by weight.

[Synthesis Example (1-3) -3]
Synthesis of NTI Uretdione Form (NTI-UD) 50 g of NTI was charged into a four-necked flask equipped with a stirrer, thermometer, and cooling tube, and 0.5 g of tris-diethylaminophosphine was added at 60 ° C. with stirring. The reaction was allowed to proceed at 60 ° C., and when the conversion to polyisocyanate became 43% by measuring the isocyanate content and the refractive index of the reaction solution, 0.4 g of phosphoric acid was added to stop the reaction. A few minutes after phosphoric acid addition, the deactivated catalyst was precipitated as crystals. Thereafter, heating was further continued at 60 ° C. for 1 hour and cooled to room temperature. The precipitate was removed by filtration to obtain a uretdione of NTI. The NCO% content of this product was 42.0% by mass. The molar ratio between the uretdione structure and the isocyanurate structure was 96: 4.

[Synthesis Example (1-3) -4]
Synthesis of uretdione form of LTI (LTI-UD)
50 g of LTI was charged into a four-necked flask equipped with a stirrer, thermometer, and cooling tube, and 0.5 g of tris-diethylaminophosphine was added at 60 ° C. while stirring. The reaction was allowed to proceed at 60 ° C., and when the conversion to polyisocyanate became 43% by measuring the isocyanate content and the refractive index of the reaction solution, 0.4 g of phosphoric acid was added to stop the reaction. A few minutes after phosphoric acid addition, the deactivated catalyst was precipitated as crystals. Thereafter, heating was further continued at 60 ° C. for 1 hour and cooled to room temperature. The precipitate was removed by filtration to obtain a uretdione of NTI. The NCO% content of this product was 39.5% by mass. The molar ratio between the uretdione structure and the isocyanurate structure was 95: 5.

[Synthesis Example (1-3) -5]
Synthesis of uretdione derivative of HDI (HDI-UD) 50 g of HDI was charged into a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, and 0.5 g of tris-diethylaminophosphine was added at 60 ° C. with stirring. The reaction was allowed to proceed at 60 ° C., and when the conversion to polyisocyanate became 43% by measuring the isocyanate content and the refractive index of the reaction solution, 0.4 g of phosphoric acid was added to stop the reaction. A few minutes after phosphoric acid addition, the deactivated catalyst was precipitated as crystals. Thereafter, heating was further continued at 60 ° C. for 1 hour and cooled to room temperature. After the precipitates were removed by filtration, the first 0.3 torr. / 155 ° C, 0.2 tor. Unreacted HDI was removed at / 145 ° C. The resulting product containing the uretdione derivative had an isocyanate group content of 23.4%. At this time, the molar ratio of the uretdione structure to the isocyanurate structure was 97: 3.

[Example (1-3) -1]
Synthesis of P (1-3) -1

The inside of the four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was set to a nitrogen atmosphere, 50 g of NTI was charged as a monomer, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 5 mg of a catalyst tetramethylammonium fluoride tetrahydrate containing 95% by mass of i-butanol was added, and the reaction was carried out. When the conversion reached 43%, dibutyl phosphoric acid was added to stop the reaction, and the polyisocyanate was added. P (1-3) -1 was obtained. The viscosity of the obtained polyisocyanate P (1-3) -1 was 59 mPa · s / 25 ° C., and the NCO content was 41.6% by mass.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-3) -1 was ○, the evaluation result of dryness was ○, and the evaluation result of adhesion to the undercoat film was ○. The results are shown in Table (1-3) -1. [Example (1-3) -5]
Synthesis of P (1-3) -5

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, 50 g of LTI was charged as a monomer, and the temperature was maintained at 60 ° C. for 2 hours. Thereafter, 5 mg of a catalyst tetramethylammonium fluoride tetrahydrate containing 95% by mass of n-butanol was added, and the reaction was carried out. When the conversion reached 42%, dibutyl phosphoric acid was added to stop the reaction. P (1-3) -5 was obtained. The viscosity of the obtained polyisocyanate P (1-3) -5 was 105 mPa · s / 25 ° C., and the NCO content was 39.5% by mass.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-3) -5 was ○, the evaluation result of dryness was ◎, and the evaluation result of adhesion to the undercoat film was ○. The results are shown in Table (1-3) -1.

[Examples (1-3) -2 to (1-3) -4, (1-3) -6 to (1-3) -7, Comparative examples (1-3) -1 to (1-3) -2]
Adjustment of P (1-3) -2 to P (1-3) -4, P (1-3) -6 to P (1-3) -9 P (1-3) -1, P (1- 3) -5, the uretdione derivative shown in Synthesis Examples (1-3) -3 to (1-3) -5, and NTI and LTI were mixed at the ratio shown in Table (1-3) -1. Thus, various polyisocyanate compositions were obtained.

Physical properties of the polyisocyanate composition were as described in Table (1-3) -1.

[Example (1-3) -8]
Synthesis of blocked polyisocyanate composition

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-3) obtained in Example (1-3) -1 was obtained. 20 g of -1 and 16.2 g of butyl acetate were charged, and the temperature was heated to 70 ° C. Thereafter, 19.6 g of 3,5-dimethylpyrazole was added with stirring, the temperature was maintained at 70 ° C, and the mixture was stirred for 1 hour. , NCO content became 0.0%, and a blocked polyisocyanate composition was obtained. The calculated NCO content of the obtained blocked polyisocyanate composition was 14.9% by mass.
Further, the degree of viscosity reduction of the obtained blocked polyisocyanate composition was ○, the evaluation result of dryness was ○, and the evaluation result of adhesion to the undercoat film was ○. These results are shown in Table (1-3) -2.

[Examples (1-3) -9 to (1-3) -10, Comparative Examples (1-3) -3 to (1-3) -4]
Synthesis of blocked polyisocyanate composition

Same as Example (1-3) -8, except that 3,5-dimethylpyrazole addition amount, butyl acetate addition amount, and type of polyisocyanate composition were as described in Table (1-3) -2. Carried out. Table (1-3) -2 shows the calculated NCO content of the obtained blocked polyisocyanate composition, the degree of viscosity reduction, the results of evaluation of dryness, and the results of evaluation of adhesion to a base coating film.

[Example (1-3) -11]
Synthesis of hydrophilic polyisocyanate composition

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-3)-obtained in Example (1-3) -1 was obtained. 1 g, and 8.4 g of a hydrophilic compound polyethylene oxide (manufactured by Nippon Emulsifier Co., Ltd., trade name: “MPG-130” number average molecular weight = 420), and the mixture was heated and stirred at 100 ° C. for 4 hours. A reactive polyisocyanate was obtained. The NCO content of the obtained hydrophilic polyisocyanate composition was 29.3% by mass.
Further, the degree of viscosity reduction was ○, the evaluation result of dryness was ○, and the evaluation result of adhesion to the undercoat film was ○.

[Examples (1-3) -12 to (1-3) -13, Comparative Examples (1-3) -5 to (1-3) -6)]
Synthesis of hydrophilic polyisocyanate composition

It carried out like Example (1-3) -11 except having added the MPG-130 addition amount and the kind of polyisocyanate composition as described in Table (1-3) -3. In addition, the NCO content, the degree of viscosity reduction, the evaluation result of dryness, and the evaluation result of adhesion to the undercoat film of the obtained hydrophilic polyisocyanate composition are shown in Table (1-3) -3.

[Example (1-3) -14]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-3) -3 obtained in Example (1-3) -3.
The degree of viscosity reduction of the polyisocyanate composition was ○, the drying property was ○, the adhesion to the undercoat film was ○, and the storage stability evaluation result was good.

[Example (1-3) -15]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-3) -3 obtained in Example (1-3) -3.
The degree of viscosity reduction of the polyisocyanate composition was ○, the drying property was ○, the adhesion to the undercoat film was ○, and the storage stability evaluation result was good.

[Synthesis Example (1-3) -6]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was set to a nitrogen atmosphere, 20 g of NTI was charged, heated to 60 ° C., 7.7 g of methanol was added, and stirring was continued. After holding for a while, an N-substituted carbamic acid ester C (1-3) -1 was obtained.

[Example (1-3) -16]

0.03 g of N-substituted carbamic acid ester C (1-3) -1 was added to 300 g of the polyisocyanate composition P (1-3) -3 obtained in Example (1-3) -3.
The degree of viscosity reduction of the polyisocyanate composition was ○, the drying property was ○, the adhesion to the undercoat film was ○, and the storage stability evaluation result was good.

  As described above, the polyisocyanate compositions of the examples to which the present invention is applied have low viscosity, and the coating compositions using the polyisocyanate compositions of the present invention have good drying properties and good adhesion to the undercoat film. It is. Furthermore, the block polyisocyanate composition or the hydrophilic polyisocyanate composition prepared from the polyisocyanate composition of the present invention has a low viscosity, and the coating composition using the composition has a drying property, It was confirmed that the adhesiveness to the film was good.

Physical properties of the polyisocyanate composition in Examples (1-4) -1 to (1-4) -16 and Comparative Examples (1-4) -1 to (1-4) -10 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<Viscosity>

As described above.
5 rpm (for 1280 mPa · s to 2560 mPa · s)

<NCO content>

As described above.

<Calculated NCO content>

As described above.

<Conversion rate>

As described above.

<Low viscosity of polyisocyanate composition (4)>

From the viscosity measurement results of the polyisocyanate mixture, the case where the temperature is less than 250 mPa · s / 25 ° C is Δ, the case where the temperature is 350 mPa · s / 25 ° C or more and less than 2000 mPa · s / 25 ° C, and the case where the temperature is 2000 mPa · s / 25 ° C or more. X.

<Method for evaluating dryness of polyisocyanate composition (3)>

An acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the polyisocyanate compositions were blended at an equivalent ratio of isocyanate group / hydroxyl group of 1.0. And butyl acetate to adjust the solid content to 50% by mass. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 23 ° C./50% RH. After a lapse of a specific time, a cotton ball (a cylindrical shape having a diameter of 2.5 cm and a height of 2.0 cm) was placed on the coating film, and a weight of 100 g was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the trace of cotton remaining on the coating film was observed. ◎ when the time when the mark disappeared completely was within 7 hours, Δ when it was more than 7 hours to 8 hours, Δ when it was more than 8 hours to less than 10 hours, and more than 10 hours. When there was, it was evaluated as x.

<Reaction rate between polyisocyanate composition and primary alcohol>

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and 50 g of Duranate (registered trademark) TKA-100 manufactured by Asahi Kasei Corporation, 33.6 g of 2-ethylhexanol, and butyl acetate were used. 83.6 g is charged and the temperature is raised to 70 ° C. The NCO content after reaching 70 ° C. is measured, and the rate of decrease in NCO groups (= reaction rate) is determined (A). Further, the inside of the four-necked flask equipped with another stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the molar ratio of the NCO group of the polyisocyanate composition to the OH group of 2-ethylhexanol was 1 Then, butyl acetate having a combined mass of the polyisocyanate composition and 2-ethylhexanol is added, and the temperature is raised to 70 ° C. The NCO content after reaching 70 ° C. is measured, and the rate of reduction of NCO groups (= reaction rate) is determined (B).
The case where (B) / (A) was 5 or more and less than 13 was evaluated as ◎, the case where more than 1 and less than 5 or more than 13 and less than 15 was evaluated as ○, and the case where 1 or less or 15 or more was evaluated as x.

<Low viscosity degree of block polyisocyanate composition (1)>

As described above.

<Method for evaluating dryness of blocked polyisocyanate composition (1)>

As described above.

<Low viscosity degree of hydrophilic polyisocyanate composition (1)>

As described above.

<Method for evaluating dryness of hydrophilic polyisocyanate composition>

As described above.

<Compatibility evaluation method with polar polyol>

Asahi Kasei Corporation's Duranol (registered trademark) T-5652, which is a polycarbonate diol, and each of the polyisocyanate compositions are blended at an equivalent ratio of isocyanate group / hydroxyl group of 1.0 so that butyl acetate has a solid content of 50% by mass. Was adjusted. After the prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, it was cured at 80 ° C. for 30 minutes, and the haze value of the coating film was measured by the following equipment.
Apparatus: Direct reading haze computer "HGM-2DP" (trade name) manufactured by Suga Test Instruments Co., Ltd.
Standard plate: The case where the haze value of the coating film of the glass plate having a thickness of 2 mm was 0.0 was 0.0, the case where the haze value was 0.1 or more and less than 0.5 was Δ, and the case where it was 0.5 or more was X.

<Storage stability evaluation method>

As described above.

[Synthesis Example (1-4) -1]
Synthesis of LTI

122.2 g of ethanolamine, 100 ml of o-dichlorobenzene, and 420 ml of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube, and ice-cooled hydrogen chloride gas was introduced. Turned into Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C. to dissolve ethanolamine hydrochloride, and hydrogen chloride gas was introduced to obtain lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 to 30 ml / min, and the reaction solution was heated to 116 ° C. and maintained at this temperature until no more water distilled. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 ml of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 120 ° C., phosgene was added at a rate of 0.4 mol / hour. Blowing was started at a constant speed and maintained for 10 hours, and then the temperature was raised to 150 ° C. The suspension almost dissolved. After cooling, the mixture was filtered, the dissolved phosgene and the solvent were distilled off under reduced pressure, and then vacuum distillation was performed to obtain 80.4 g of a colorless and transparent LTI having a boiling point of 155 to 157 ° C / 0.022 mmHg. Its NCO content was 47.1% by weight.

[Synthesis Example (1-4) -2]
Synthesis of GTI

275 g of glutamate hydrochloride, 800 g of ethanolamine hydrochloride, and 150 ml of toluene are placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. At reflux for 24 hours. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 270 g of bis (2-aminoethyl) glutamate trihydrochloride. 85 g of this bis (2-aminoethyl) glutamate trihydrochloride was suspended in 680 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 135 ° C., phosgene was added at a rate of 0.8 mol / hour. The reaction product was filtered, concentrated under reduced pressure, and purified by a thin-film evaporator to obtain 54 g of GTI. The NCO content was 39.8% by weight.

[Synthesis Example (1-4) -3]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, thermometer and gas inlet tube, 1,060 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter referred to as triamine) was dissolved in 1500 g of methanol, and 35% concentrated hydrochloric acid was added thereto. 1800 ml was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. The obtained triamine hydrochloride (650 g) was suspended as fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / Hr. Then, the temperature was further increased and maintained at 180 ° C., and phosgene was continuously blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, vacuum distillation was performed to obtain 420 g of colorless and transparent NTI having a boiling point of 161 to 163 ° C / 1.2 mmHg. Its NCO content was 50.0% by weight.

[Example (1-4) -1]
Synthesis of P (1-4) -1

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, 50 g of LTI and 0.05 g of isobutanol were charged as monomers, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 5 mg of benzyltrimethylammonium hydroxide, an isocyanurate-forming catalyst, was added, and an isocyanurate-forming reaction was performed. When the conversion reached 12%, dibutylphosphoric acid was added to stop the reaction. The reaction liquid was further kept at 120 ° C. for 15 minutes to obtain a polyisocyanate composition P (1-4) -1. The viscosity of the polyisocyanate composition P (1-4) -1 was 37 mPa · s / 25 ° C., and the NCO content was 45.4% by mass.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-4) -1 is ○, the evaluation result of dryness is △, the result of the reaction rate between the polyisocyanate composition and the primary alcohol is ○, the compatibility with the polar polyol The evaluation result was ○. These results are shown in Table (1-4) -1.

[Examples (1-4) -2 to (1-4) -8, Comparative Examples (1-4) -1, (1-4) -2]

It carried out similarly to Example (1-4) -1 except having set the monomer, the catalyst, the terminator, the reaction temperature, and the conversion of Table (1-4) -1 as described. In addition, Table (1-4) -1 shows the viscosity, NCO content, degree of viscosity reduction, results of evaluation of dryness, and results of evaluation of compatibility with polar polyols of the obtained polyisocyanate composition.

[Comparative Example (1-4) -3]

The reaction solution obtained in Comparative Example (1-4) -2 was fed to a thin film evaporator, and unreacted HDI was removed to obtain a polyisocyanate composition P (1-4) -12. The viscosity of the obtained polyisocyanate composition P (1-4) -12 was 2300 mPa · s / 25 ° C., and the NCO content was 21.5% by mass.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-4) -12 was ×, the evaluation result of dryness was ○, the result of the reaction rate between the polyisocyanate composition and the primary alcohol was ×, and the compatibility with the polar polyol was The evaluation result was x. These results are shown in Table (1-4) -1.

[Comparative Example (1-4) -4]

The LTI synthesized in Synthesis Example (1-4) -1 was used alone. The degree of viscosity reduction of the LTI was ○, the evaluation result of dryness was ×, the result of the reaction rate between the polyisocyanate composition and the primary alcohol was ○, and the evaluation result of compatibility with the polar polyol was ○. These results are shown in Table (1-4) -1.

[Example (1-4) -9]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, 50 g of LTI was charged as a monomer, the temperature was heated to 50 ° C., and then 29.3 g of methyl ethyl ketoxime was stirred. Was added dropwise and kept at 50 ° C. for 1 hour. Next, 0.05 g of isobutanol was charged, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 5 mg of isocyanurate-forming catalyst tetramethylammonium capric acid was added, and an isocyanurate-forming reaction was performed. When the conversion reached 40%, phosphoric acid was added to stop the reaction. Thereafter, the temperature was raised to 150 ° C., and methyl ethyl ketoxime was distilled off by vacuum distillation to obtain a polyisocyanate composition P (1-4) -9. The viscosity of the obtained P (1-4) -9 was 123 mPa · s / 25 ° C., and the NCO content was 42.1% by mass.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-4) -9 was ○, the evaluation result of dryness was ◎, the result of the reaction rate between the polyisocyanate composition and the primary alcohol was ◎, and the compatibility with the polar polyol was The evaluation result was ○.

In the above Table (1-4) -1, the catalyst and the terminator described in the abbreviations respectively mean the following materials.
BTMA-H: benzyltrimethylammonium hydroxide.
BTMA-A: benzyltrimethylammonium capric acid.
TMA-A: tetramethylammonium capric acid.
DBP: dibutyl phosphoric acid.

[Example (1-4) -10]

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-4)-obtained in Example (1-4) -4. 4, 20 g of butyl acetate and 16.1 g of butyl acetate were added, and the temperature was heated to 70 ° C. Thereafter, 19.5 g of 3,5-dimethylpyrazole was added with stirring, the temperature was maintained at 70 ° C, and the mixture was stirred for 1 hour. The NCO content became 0.0%, and a blocked polyisocyanate composition was obtained. The viscosity of the obtained blocked polyisocyanate composition was 540 mPa · s / 25 ° C., and the calculated NCO content was 14.9% by mass.
Further, the obtained blocked polyisocyanate composition had a degree of viscosity reduction of ○, a dryness evaluation result of ○, and a compatibility evaluation result with a polar polyol of ○. These results are shown in Table (1-4) -2.

[Example (1-4) -11, Comparative examples (1-4) -5 to (1-4) -7]

The procedure was performed in the same manner as in Example (1-4) -10, except that the addition amount of 3,5-dimethylpyrazole and the addition amount of butyl acetate in Table (1-4) -2 were as described. Table (1-4) -2 shows the viscosity, calculated NCO content, reduced viscosity, dryness evaluation result, and compatibility evaluation result with the polar polyol of the obtained blocked polyisocyanate composition.

[Example (1-4) -12]

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-4)-obtained in Example (1-4) -4. 20 g, and 8.3 g of a hydrophilic compound, polyethylene oxide (manufactured by Nippon Emulsifier Co., Ltd., trade name: “MPG-130”, number average molecular weight = 420), and kept at 100 ° C. for 4 hours while heating and stirring. A reactive polyisocyanate was obtained. The viscosity of the obtained hydrophilic polyisocyanate composition was 110 mPa · s / 25 ° C., and the NCO content was 26.3% by mass.
Further, the degree of viscosity reduction was ○, and the evaluation result of dryness was ○.

[Example (1-4) -13, Comparative examples (1-4) -8 to (1-4) -10]

The operation was carried out in the same manner as in Example (1-4) -9, except that the amount of MPG-130 added in Table (1-4) -3 was as described. In addition, the viscosity, NCO content, degree of viscosity reduction, and dryness evaluation results of the obtained hydrophilic polyisocyanate composition are described in Table (1-4) -3.

[Example (1-4) -14]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-4) -1 obtained in Example (1-4) -1.
The degree of viscosity reduction of this polyisocyanate composition is ○, the result of evaluation of dryness is △, the result of reaction rate between polyisocyanate composition and primary alcohol is ○, the result of compatibility evaluation with polar polyol is ○, storage stability evaluation The results were good.

[Example (1-4) -15]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-4) -1 obtained in Example (1-4) -1.
The degree of viscosity reduction of this polyisocyanate composition is ○, the result of evaluation of dryness is △, the result of reaction rate between polyisocyanate composition and primary alcohol is ○, the result of compatibility evaluation with polar polyol is ○, storage stability evaluation The results were good.

[Synthesis Example (1-4) -4]

The inside of the four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was set to a nitrogen atmosphere, 20 g of LTI was charged, heated to 60 ° C., 7.2 g of methanol was added, and stirring was continued for 4 hours. Retained to obtain N-substituted carbamic acid ester C (1-4) -1.

[Example (1-4) -16]

0.03 g of N-substituted carbamic acid ester C (1-4) -1 was added to 300 g of the polyisocyanate composition P (1-4) -1 obtained in Example (1-4) -1.
The degree of viscosity reduction of this polyisocyanate composition is ○, the result of evaluation of dryness is △, the result of reaction rate between polyisocyanate composition and primary alcohol is ○, the result of compatibility evaluation with polar polyol is ○, storage stability evaluation The results were good.

  As described above, the polyisocyanate composition, the blocked polyisocyanate composition, or the hydrophilic polyisocyanate composition of each of the examples to which the present invention is applied has a low viscosity, and has excellent drying properties and compatibility with a polar polyol. It was confirmed that.

Physical properties of the polyisocyanate composition in Examples (1-5) -1 to (1-5) -13 and Comparative Examples (1-5) -1 to (1-5) -3 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<Number of nitrogen elements derived from isocyanate group and contained in allophanate structure>

By ¹³ C-NMR measurement using Biospin Avance 600 (trade name) manufactured by Bruker, the ratio of the carbon element adjacent to the isocyanate group-derived structure and the allophanate structure was determined, and the nitrogen contained in each structure was determined from this. The number of elements was calculated and determined. The peak position of each functional group and structure is shown for NTI. However, since the peak position is changed by triisocyanate, calibration was performed using a standard substance or the like as appropriate.
Here, the structure derived from the isocyanate group means an isocyanate group, an allophanate structure, an isocyanurate structure, a uretdione structure, an iminooxadiazinedione structure, a urethane structure, and a burette structure.

Specific measurement conditions were as follows.
¹³ C-NMR apparatus: AVANCE600 (manufactured by Bruker)
Cryoprobe (Bruker)
Cryo Probe
CPDUL
600S3-C / HD-05Z
Resonant frequency: 150MHz
Concentration: 60 wt / vol%
Shift standard: CDCl ₃ (77 ppm)
Number of integration: 10000 times Pulse program: zgpg30 (proton complete decoupling method, waiting time 2 sec) The integrated value of the signal below is divided by the number of carbons being measured, multiplied by the number of nitrogen contained in the structure, and the value is multiplied. Was used to determine the ratio of the number of nitrogen elements.
Isocyanate group: around 121.5 ppm: integrated value ÷ 1 × 1
Uretdione structure: around 157.5 ppm: integral value ÷ 2 × 2
Iminooxadiazinedione structure: around 144.5 ppm: integrated value ÷ 1 × 3
Isocyanurate structure: around 148.5 ppm: integrated value ÷ 3 × 3
Allophanate structure: around 154 ppm: integrated value ÷ 1 × 2
Urethane structure: around 156.3 ppm: integral value ÷ 1 × 1
Bullet structure: around 156.1 ppm: integral value ÷ 2 × 3

<Viscosity>
The viscosity was measured at 25 ° C. using an E-type viscometer (manufactured by Tokimec). In the measurement, a standard rotor (1 ° 34 ′ × R24) was used. The rotation speed is as follows.
100rpm (less than 128mPa · s)
50 rpm (128 mPa · s to 256 mPa · s)
20 rpm (in the case of 256 mPa · s to 640 mPa · s)
10 rpm (for 640 mPa · s to 1280 mPa · s)
5 rpm (for 1280 mPa · s to 2560 mPa · s)
In addition, the nonvolatile content of the polyisocyanate compositions produced in each of the following Examples and Comparative Examples was examined by the method described below, and those having a value of 98% by mass or more were measured as they were.

<NCO content>

As described above.

<Conversion rate>

As described above.

<Degree of viscosity reduction of polyisocyanate composition (5)>

From the viscosity measurement results of the polyisocyanate mixture, the case of 100 mPa · s / 25 ° C or less is Δ, the case of more than 100 mPa · s / 25 ° C is 300 mPa · s / 25 ° C or less, and the case of exceeding 300 mPa · s / 25 ° C. X.

<Method for evaluating dryness of polyisocyanate composition (4)>

An acrylic polyol (trade name “SETALUX1753” of Nuplex Resin, resin concentration 70%, hydroxyl value 138.6 mgKOH / g) and each of the polyisocyanate compositions were blended at an equivalent ratio of isocyanate group / hydroxyl group of 1.0. And butyl acetate to adjust the solid content to 50% by mass. The prepared coating composition was applied on a glass plate so as to have a dry film thickness of 40 μm, and then cured at 23 ° C./50% RH. After a lapse of a specific time, a cotton ball (a cylindrical shape having a diameter of 2.5 cm and a height of 2.0 cm) was placed on the coating film, and a weight of 100 g was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the trace of cotton remaining on the coating film was observed. The case where the time when the trace was completely invisible was within 11 hours, the case where it was more than 11 hours to 13 hours, and the case where it was more than 13 hours was x.

<Lower viscosity of blocked polyisocyanate composition (3)>

From the results of the viscosity measurement of the blocked polyisocyanate composition, the case where the viscosity was less than 500 mPa · s / 25 ° C. was evaluated as Δ, and the case where the viscosity was 500 mPa · s / 25 ° C. or more was evaluated as x.

<Method for evaluating dryness of blocked polyisocyanate composition (1)>

As described above.

<Low viscosity of hydrophilic polyisocyanate composition (3)>

From the results of the viscosity measurement of the hydrophilic polyisocyanate composition, the case where the viscosity was 200 mPa · s / 25 ° C. or less was evaluated as Δ, and the case where the viscosity exceeded 200 mPa · s / 25 ° C. was evaluated as ×.

<Method for evaluating dryness of hydrophilic polyisocyanate composition>

As described above.

<Solubility in low-polarity organic solvents (1)>

At 23 ° C., 100 g of HAWS (aniline point: 15 ° C.) was added to 100 g of the polyisocyanate composition, and the state after standing for 12 hours was observed.場合 indicates uniformity, X indicates separation or cloudiness, and Δ indicates slight cloudiness.

<Dispersibility in water>

One part of the polyisocyanate composition was added to 100 parts of a mixture of 23 ° C. water / BGA = 9: 1, and the mixture was vigorously stirred and dispersed by hand. After 3 hours, the state was observed. After 3 hours, those which were uniformly dispersed were evaluated as ○, those with slight precipitation were evaluated as Δ, and those separated were evaluated as ×.

<Storage stability evaluation method>

As described above.

[Synthesis Example (1-5) -1]
Synthesis of LTI

122.2 g of ethanolamine, 100 ml of o-dichlorobenzene, and 420 ml of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube, and ice-cooled hydrogen chloride gas was introduced. Converted to salt. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C. to dissolve ethanolamine hydrochloride, and hydrogen chloride gas was introduced to obtain lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 to 30 ml / min, and the reaction solution was heated to 116 ° C. and maintained at this temperature until no more water distilled. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 ml of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 120 ° C., phosgene was added at a rate of 0.4 mol / hour. Blowing was started at a constant speed and maintained for 10 hours, and then the temperature was raised to 150 ° C. The suspension almost dissolved. After cooling and filtration, the dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation to obtain 80.4 g of a colorless and transparent LTI having a boiling point of 155 to 157 ° C / 0.022 mmHg. Its NCO content was 47.1% by weight.

[Synthesis Example (1-5) -2]
Synthesis of GTI

275 g of glutamate hydrochloride, 800 g of ethanolamine hydrochloride, and 150 ml of toluene are placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. The mixture was heated at reflux at 24 ° C. for 24 hours. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 270 g of bis (2-aminoethyl) glutamate trihydrochloride. 85 g of this bis (2-aminoethyl) glutamate trihydrochloride was suspended in 680 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 135 ° C., phosgene was added at a rate of 0.8 mol / hour. The reaction product was filtered, concentrated under reduced pressure, and further purified by a thin film evaporator to obtain 54 g of GTI. The NCO content was 39.8% by weight.

[Synthesis Example (1-5) -3]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, 1,060 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter, referred to as triamine) was dissolved in 1500 g of methanol, and 35% concentrated. 1800 ml of hydrochloric acid was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. The obtained triamine hydrochloride (650 g) was suspended as fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / Hr. Then, the temperature was further increased and maintained at 180 ° C., and phosgene was continuously blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, vacuum distillation is performed to obtain colorless and transparent 4-isocyanatomethyl-1,8-octamethylene diisocyanate having a boiling point of 161 to 163 ° C./1.2 mmHg (hereinafter “NTI”). 420 g was obtained, which had an NCO content of 50% by weight.

[Example (1-5) -1]
Synthesis of P (1-5) -1

The inside of the four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was set to a nitrogen atmosphere, 50 g of NTI and 11.7 g of 2-ethylhexanol were charged as monomers, and the temperature was maintained at 90 ° C. for 1 hour. . Thereafter, the temperature was raised to 130 ° C., and a 20% solids mineral spirit solution of zirconyl 2-ethylhexanoate, an allophanation catalyst (trade name “Nikka Octix Zirconium 13%” manufactured by Nippon Chemical Industry Co., Ltd., diluted with mineral spirit) Was added, and an allophanate-forming reaction was performed. When the conversion reached 10%, a 50% solid solution of pyrophosphoric acid in isobutanol (a reagent manufactured by Katayama Chemical Industry Co., Ltd. diluted with isobutanol) was added, and the reaction was performed. Was stopped to obtain polyisocyanate P (1-5) -1. The viscosity of the obtained polyisocyanate P (1-5) -1 was 35 mPa · s / 25 ° C., and the NCO content was 39% by mass.
Furthermore, the degree of viscosity reduction of the polyisocyanate composition P (1-5) -1 was ○, the evaluation result of dryness was ○, the result of solubility in a low-polarity organic solvent was ○, and the dispersibility in water was ○. Was.

[Examples (1-5) -2 to (1-5) -8, Comparative examples (1-5) -1 to (1-5) -3]

The procedure was performed in the same manner as in Example (1-5) -1 except that the types and charged amounts of the monomer and alcohol and the conversion were as shown in Table (1-5) -1. However, in Comparative Example (1-5) -3, the residual HDI was removed by thin-film distillation until the residual HDI became 0.5% by mass. Table (1-5) -1 shows the results of the viscosity, NCO content, degree of viscosity reduction, drying property evaluation, solubility in low-polar organic solvents, and dispersibility in water of the obtained polyisocyanate composition. Described.

[Example (1-5) -9]

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-5) obtained in Example (1-5) -7 was obtained. -20 g of -7 and 15.5 g of butyl acetate were charged, and the temperature was heated to 70 ° C. Thereafter, 17.9 g of 3,5-dimethylpyrazole was added with stirring, the temperature was maintained at 70 ° C, and the mixture was stirred for 1 hour. , NCO content became 0.0%, and a blocked polyisocyanate was obtained. The viscosity of the obtained blocked polyisocyanate was 360 mPa · s / 25 ° C.
Further, the degree of viscosity reduction was ○, and the evaluation result of dryness was ○.

[Example (1-5) -10]

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-5) obtained in Example (1-5) -7 was obtained. -20 g of -7 and 8.3 g of polyethylene oxide as a hydrophilic compound (manufactured by Nippon Emulsifier Co., Ltd., trade name “MPG-130” number average molecular weight = 420), and the mixture was heated and stirred at 100 ° C. for 4 hours. A hydrophilic polyisocyanate was obtained. The viscosity of the obtained hydrophilic polyisocyanate was 85 mPa · s / 25 ° C.
Further, the degree of viscosity reduction was ○, and the evaluation result of dryness was ○.

[Example (1-5) -11]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-5) -1 obtained in Example (1-5) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, the evaluation result of dryness was ○, the result of solubility in a low-polarity organic solvent was ○, the dispersibility in water was ○, and the storage stability evaluation result was good .

[Example (1-5) -12]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-5) -1 obtained in Example (1-5) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, the evaluation result of dryness was ○, the result of solubility in a low-polarity organic solvent was ○, the dispersibility in water was ○, and the storage stability evaluation result was good .

[Synthesis Example (1-5) -4]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was set to a nitrogen atmosphere, 20 g of NTI was charged, heated to 60 ° C., 7.7 g of methanol was added, and stirring was continued. After holding for a time, an N-substituted carbamic acid ester C (1-5) -1 was obtained.

[Example (1-5) -13]

0.03 g of N-substituted carbamic acid ester C (1-5) -1 was added to 300 g of the polyisocyanate composition P (1-5) -1 obtained in Example (1-5) -1.
The degree of viscosity reduction of this polyisocyanate composition was ○, the evaluation result of dryness was ○, the result of solubility in a low-polarity organic solvent was ○, the dispersibility in water was ○, and the storage stability evaluation result was good .

The physical properties of the polyisocyanate composition in Examples (1-6) -1 to (1-6) -11 and Comparative Examples (1-6) -1 to (1-6) -10 were measured as follows. . Unless otherwise specified, “parts” and “%” mean “parts by mass” and “% by mass”.

<Viscosity>

As described above.

<NCO content>

As described above.

<Calculated NCO content>

As described above.

<Conversion rate>

As described above.

<Method for determining molar ratio of allophanate structure>

Using a Bruker Co. Biospin AVANCE 600 (trade ^name), 13 to measure the C-NMR, it was determined iminooxadiazinedione structure, uretdione, isocyanurate structures, allophanate structures, urethane structures, and the molar ratio of biuret structure .
Specific measurement conditions were as follows.
¹³ C-NMR apparatus: AVANCE600 (manufactured by Bruker)
Cryoprobe (Bruker)
Cryo Probe
CPDUL
600S3-C / HD-05Z
Resonant frequency: 150MHz
Concentration: 60 wt / vol%
Shift standard: CDCl ₃ (77 ppm)
Number of integration: 10000 times Pulse program: zgpg30 (proton complete decoupling method, waiting time 2 sec)

The integral value of the following signal was divided by the number of measured carbons, and each molar ratio was determined from the value.
Uretdione structure: around 157.5 ppm: integral value ÷ 2
Iminooxadiazinedione structure: around 144.5 ppm: integral value ÷ 1
Isocyanurate structure: around 148.5 ppm: integral value ÷ 3
Allophanate structure: around 154 ppm: integrated value ÷ 1
Urethane structure: around 156.3 ppm: integral value ÷ 1-allophanate structure integral value Bullet structure: around 156.1 ppm: integral value ÷ 2
The molar ratios of the allophanate structure, uretdione structure, iminooxadiazinedione structure, isocyanurate structure, urethane structure, and burette structure are a, b, c, d, e, and f, and the molar ratio of the allophanate structure is represented by the following formula. The ratio was determined.
Molar ratio of allophanate structure = a / (a + b + c + d + e + f)

<Low viscosity of polyisocyanate composition (4)>
As described above.

<Method for evaluating dryness of polyisocyanate composition (3)>

As described above.

<Reaction rate between polyisocyanate composition and primary alcohol>

As described above.

<Low viscosity of block polyisocyanate composition (4)>

From the viscosity measurement results of the blocked polyisocyanate composition, the case where the viscosity was less than 450 mPa · s / 25 ° C. was evaluated as “○”, and the case where the viscosity was 450 mPa · s / 25 ° C. or higher was evaluated as “X”.

<Method for evaluating dryness of blocked polyisocyanate composition (1)>

As described above.

<Low viscosity (4) of hydrophilic polyisocyanate composition>

From the results of the viscosity measurement of the hydrophilic polyisocyanate composition, the case where the viscosity was less than 90 mPa · s / 25 ° C. was evaluated as “good”, and the case where the viscosity was 90 mPa · s / 25 ° C. or more was evaluated as “bad”.

<Method for evaluating dryness of hydrophilic polyisocyanate composition>

As described above.

<Solubility in low-polarity organic solvents (2)>

Under a condition of 0 ° C., 100 g of High Aromatic White Spirit (HAWS) (aniline point: 15 ° C.) is added to 100 g of the polyisocyanate composition, and the state after standing for 24 hours is observed. I judged that it was. The case where the mixture was uniformly mixed was evaluated as ○, and the case where separation or cloudiness was observed was evaluated as ×.

<Storage stability evaluation method>

As described above.

[Synthesis Example (1-6) -1]
Synthesis of LTI

122.2 g of ethanolamine, 100 mL of o-dichlorobenzene, and 420 mL of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube, and ice-cooled hydrogen chloride gas was introduced. Converted to salt. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C. to dissolve ethanolamine hydrochloride, and hydrogen chloride gas was introduced to obtain lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 to 30 mL / min, and the reaction solution was heated to 116 ° C. and maintained at this temperature until no more water distilled. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 mL of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 120 ° C., phosgene was added at a rate of 0.4 mol / hour. Blowing was started at a constant speed and maintained for 10 hours, and then the temperature was raised to 150 ° C. The suspension almost dissolved. After cooling, the mixture was filtered, and the dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation to obtain 80.4 g of a colorless and transparent LTI having a boiling point of 155 to 157 ° C / 0.022 mmHg. Its NCO content was 47.1% by weight.

[Synthesis Example (1-6) -2]
Synthesis of GTI

Glutamic acid hydrochloride (275 g), ethanolamine hydrochloride (800 g), and toluene (150 mL) are placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. The mixture was heated at reflux at 24 ° C. for 24 hours. The resulting reaction mixture was recrystallized in a mixture of methanol and ethanol to obtain 270 g of bis (2-aminoethyl) glutamate trihydrochloride. 85 g of this bis (2-aminoethyl) glutamate trihydrochloride was suspended in 680 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 135 ° C., phosgene was added at a rate of 0.8 mol / hour. The reaction product was filtered, concentrated under reduced pressure, and further purified by a thin film evaporator to obtain 54 g of GTI. The NCO content was 39.8% by weight.

[Synthesis Example (1-6) -3]
Synthesis of NTI

In a four-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, 1,060 g of 4-aminomethyl-1,8-octamethylenediamine (hereinafter sometimes referred to as "triamine") was added to 1500 g of methanol. The solution was dissolved, and 1800 mL of 35% concentrated hydrochloric acid was gradually added dropwise while cooling. After removing methanol and water under reduced pressure, the mixture was concentrated, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid. The obtained triamine hydrochloride (650 g) was suspended as fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / Hr. Then, the temperature was further increased and maintained at 180 ° C., and phosgene was continuously blown in for 12 hours. After distilling out the dissolved phosgene and the solvent under reduced pressure, the residue was distilled under vacuum to obtain colorless and transparent 4-isocyanatomethyl-1,8-octanemethylene diisocyanate having a boiling point of 161 to 163 ° C./1.2 mmHg (hereinafter referred to as “NTI ) Was obtained.) 420 g was obtained. Its NCO content was 50.0% by weight.

[Example (1-6) -1]
Synthesis of P (1-6) -1

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was set to a nitrogen atmosphere, 50 g of LTI and 2.0 g of 2-ethylhexanol were charged as monomers, and the temperature was maintained at 90 ° C. for 1 hour. . Thereafter, the temperature was raised to 130 ° C., and a 20% solids mineral spirit solution of zirconyl 2-ethylhexanoate, an allophanation catalyst (trade name “Nikka Octix Zirconium 13%” manufactured by Nippon Chemical Industry Co., Ltd., diluted with mineral spirit) Was added, and an allophanate-forming reaction was performed. When the conversion reached 20%, a 50% solid solution of pyrophosphoric acid in isobutanol (a reagent manufactured by Katayama Chemical Co., Ltd. was diluted with isobutanol). Was added to stop the reaction to obtain polyisocyanate P (1-6) -1. The viscosity of the obtained polyisocyanate P (1-6) -1 was 46 mPa · s / 25 ° C., the NCO content was 42% by mass, and the molar ratio of the allophanate structure was 0.75.
Furthermore, the degree of viscosity reduction of the polyisocyanate composition P (1-6) -1 is ○, the evaluation result of drying property is ○, the result of the reaction rate between the polyisocyanate composition and the primary alcohol is ○, The solubility result was ○. The results are shown in Table (1-6) -1.

[Examples (1-6) -2 to (1-6) -5, Comparative examples (1-6) -1 and 2]
Synthesis of P (1-6) -2 to P (1-6) -5, P (1-6) -7, P (1-6) -8

The procedure was performed in the same manner as in Example (1-6) -1 except that the monomers, the charged amount of 2-ethylhexanol, and the conversion in Table (1-6) -1 were as described. Table (1-6) -1 shows the viscosity, NCO content, molar ratio of allophanate structure, degree of viscosity reduction, results of dryness evaluation, and results of solubility in low-polarity organic solvents of the obtained polyisocyanate composition. It described in.

[Example (1-6) -6]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, 50 g of LTI was charged as a monomer, the temperature was heated to 50 ° C., and then 29.3 g of methyl ethyl ketoxime was stirred. Was added dropwise and kept at 50 ° C. for 1 hour. Next, 4.0 g of 2-ethylhexanol was charged, and the temperature was maintained at 90 ° C. for 1 hour. Thereafter, the temperature was raised to 130 ° C., and a 20% solids mineral spirit solution of zirconyl 2-ethylhexanoate, an allophanation catalyst (trade name “Nikka Octix Zirconium 13%” manufactured by Nippon Chemical Industry Co., Ltd., diluted with mineral spirit) Was added, and an allophanate-forming reaction was carried out. When the conversion reached 40%, a 50% solid solution of pyrophosphoric acid in isobutanol (a reagent manufactured by Katayama Chemical Industry Co., Ltd. was diluted with isobutanol) was added. The reaction was stopped, then the temperature was raised to 150 ° C., and the mixture was distilled under vacuum to distill out methyl ethyl ketoxime, thereby obtaining a polyisocyanate composition P (1-6) -6. The viscosity of the obtained P (1-6) -6 was 79 mPa · s / 25 ° C., the NCO content was 39% by mass, and the mole ratio of the allophanate structure was 0.81. Further, the degree of viscosity reduction of the polyisocyanate composition P (1-6) -5 was ○, the evaluation result of dryness was ◎, the result of the reaction rate between the polyisocyanate composition and the primary alcohol was ◎, The solubility result was ○.

[Comparative Example (1-6) -3]
Synthesis of P (1-6) -9

The reaction solution obtained in Comparative Example (1-6) -2 was fed to a thin film evaporator to remove unreacted HDI, to obtain a polyisocyanate composition P (1-6) -9. The viscosity of the obtained polyisocyanate composition P (1-6) -9 was 25 mPa · s / 25 ° C., the NCO content was 47% by mass, and the molar ratio of the allophanate structure was 0.87.
Further, the degree of viscosity reduction of the polyisocyanate composition P (1-6) -9 was x, the result of the evaluation of dryness was x, the result of the reaction rate of the polyisocyanate composition and the primary alcohol was x, The solubility result was ○. The results are shown in Table (1-6) -1.

[Comparative Example (1-6) -4]

The viscosity of the LTI monomer was 25 mPa · s / 25 ° C., the NCO content was 47% by mass, and the mole ratio of the allophanate structure was 0.
Further, the degree of viscosity reduction of the LTI monomer was ○, the evaluation result of dryness was ×, the result of the reaction rate between the polyisocyanate composition and the primary alcohol was ○, and the result of solubility in the low polar organic solvent was ○. The results are shown in Table (1-6) -1.

[Example (1-6) -7]
Synthesis of blocked polyisocyanate composition

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-6) obtained in Example (1-6) -4 was obtained. -20 g of -4 and 15.5 g of butyl acetate were charged, and the temperature was heated to 70 ° C. Then, 17.9 g of 3,5-dimethylpyrazole was added with stirring, the temperature was maintained at 70 ° C, and the mixture was stirred for 1 hour. , NCO content became 0.0%, and a blocked polyisocyanate was obtained. The viscosity of the obtained blocked polyisocyanate was 360 mPa · s / 25 ° C., and the calculated NCO content was 14.2% by mass.
Further, the degree of viscosity reduction was ○, and the evaluation result of dryness was ○. These results are shown in Table (1-6) -2.

[Comparative Example (1-6) -5 to (1-6) -7]
Synthesis of blocked polyisocyanate composition

It carried out like Example (1-6) -7 except having set the polyisocyanate composition of Table (1-6) -2, the amount of 3,5-dimethylpyrazole addition, and the amount of butyl acetate addition as described. In addition, Table (1-6) -2 shows the viscosity, calculated NCO content, reduced viscosity, and dryness evaluation results of the obtained blocked polyisocyanate composition.

[Example (1-6) -8]
Synthesis of hydrophilic polyisocyanate composition

The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was set to a nitrogen atmosphere, and the polyisocyanate composition P (1-6)-obtained in Example (1-6) -4. 20 g, and 8.3 g of a hydrophilic compound, polyethylene oxide (manufactured by Nippon Emulsifier Co., Ltd., trade name: “MPG-130”, number average molecular weight = 420), and kept at 100 ° C. for 4 hours while heating and stirring. A reactive polyisocyanate was obtained. The viscosity of the obtained hydrophilic polyisocyanate was 84 mPa · s / 25 ° C., and the NCO content was 24.8% by mass.
Further, the degree of viscosity reduction was ○, and the evaluation result of dryness was ○. The results are shown in Table (1-6) -3.

[Comparative Examples (1-6) -8 to (1-6) -10]
Synthesis of hydrophilic polyisocyanate composition

It carried out similarly to Example (1-6) -8 except having set the polyisocyanate composition of Table (1-6) -3, and the addition amount of MPG-130 as described. In addition, Table (1-6) -3 shows the viscosity, NCO content, viscosity reduction degree, and dryness evaluation results of the obtained hydrophilic polyisocyanate composition.

[Example (1-6) -9]

0.03 g of 2,2,4-trimethylpentane was added to 300 g of the polyisocyanate composition P (1-6) -1 obtained in Example (1-6) -1.
The degree of viscosity reduction of this polyisocyanate composition is ○, the evaluation result of dryness is ○, the result of reaction rate between polyisocyanate composition and primary alcohol is ○, the result of solubility in low polar organic solvent is 、, storage stability The evaluation result was good.

[Example (1-6) -10]

0.03 g of hexadecane was added to 300 g of the polyisocyanate composition P (1-6) -1 obtained in Example (1-6) -1.
The degree of viscosity reduction of this polyisocyanate composition is ○, the evaluation result of dryness is ○, the result of reaction rate between polyisocyanate composition and primary alcohol is ○, the result of solubility in low polar organic solvent is 、, storage stability The evaluation result was good.

[Synthesis Example (1-6) -4]
Synthesis of C (1-6) -1

The inside of the four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen blowing tube was set to a nitrogen atmosphere, 20 g of LTI was charged, heated to 60 ° C., 7.2 g of methanol was added, and stirring was continued for 4 hours Retained to give N-substituted carbamic acid ester C (1-6) -1.

[Example (1-6) -11]

0.03 g of N-substituted carbamic acid ester C (1-6) -1 was added to 300 g of the polyisocyanate composition P (1-6) -1 obtained in Example (1-6) -1.
The degree of viscosity reduction of this polyisocyanate composition is ○, the evaluation result of dryness is ○, the result of reaction rate between polyisocyanate composition and primary alcohol is ○, the result of solubility in low polar organic solvent is 、, storage stability The evaluation result was good.

From the above, it was confirmed that the polyisocyanate compositions of the respective examples had low viscosity, and were excellent in drying properties and solubility in low-polarity organic solvents.

Claims (32)

A polyisocyanate composition comprising a polyisocyanate compound represented by the general formula (I), (II), (III) or (IV).

[In general formulas (I), (II), (III) and (IV), a plurality of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ are each independently an organic group, and a plurality of R ¹¹ , R ^At least one of R ³¹ and R ⁴¹ is a group represented by formula (V) or (VI), and at least one of a plurality of R ²¹ is a group represented by formula (V). A plurality of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ may be the same or different. In the general formula (III), R ³² is a residue obtained by removing one hydroxy group from a monohydric or higher alcohol. "

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond. ] The polyisocyanate composition according to claim 1, comprising a polyisocyanate compound represented by the general formula (I) and the general formula (II).

[In the general formulas (I) and (II), a plurality of R ¹¹ and R ²¹ are each independently an organic group, and at least one of the plurality of R ¹¹ and R ²¹ is a group represented by the general formula (V) Is a group represented by A plurality of R ¹¹ and R ²¹ may be the same or different. ]

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ] Including a polyisocyanate compound represented by the general formula (I) and the general formula (II),
The polyisocyanate composition according to claim 2, wherein the molar ratio between the iminooxadiazinedione structure and the isocyanurate structure is 0.01 or more and 1.5 or less. The polyisocyanate composition according to claim 2, further comprising a triisocyanate represented by the general formula (V) -1.

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]   The method according to any one of claims 2 to 4, comprising a polyisocyanate compound represented by the general formula (II), wherein the theoretical reaction rate calculated from NCO% of the polyisocyanate composition is 47% or less. A polyisocyanate composition. The polyisocyanate compound represented by the general formula (II), wherein the theoretical reaction rate calculated from the NCO% of the polyisocyanate composition is 95% or more and 150% or less. Item 13. The polyisocyanate composition according to item 8. A polyisocyanate composition comprising a polyisocyanate compound (A) represented by the general formula (II) and a triisocyanate compound (B) represented by the general formula (V) -1;
The peak area (A) of the number average molecular weight of the polyisocyanate compound (A) and the peak area (B) of the number average molecular weight of the triisocyanate compound (B) obtained by gel permeation chromatography (GPC) measurement. The polyisocyanate composition according to claim 4, wherein the area ratio ((A) / [(A) + (B)]) is 0.8 or more and less than 1. When a monomer trimer in which all of R ^{21 in} the general formula (II) is a triisocyanate represented by the general formula (V) is a compound (C), the monomer trimer is obtained by gel permeation chromatography (GPC) measurement. The peak area (A) of the number average molecular weight of the polyisocyanate compound (A), the peak area (B) of the number average molecular weight of the triisocyanate compound (B), and the number average molecular weight of the compound (C). The polyisocyanate composition according to claim 7, wherein the area ratio ((C) / [(A) + (B)]) to the peak area (C) is 0.3 or more and less than 1.   The polyisocyanate composition according to claim 7 or 8, wherein the isocyanate group functionality is 4 or more and 12 or less. The polyisocyanate compound represented by the general formula (II) and the general formula (III), wherein the molar ratio of the isocyanurate structure to the allophanate structure is from 100 / 0.1 to 100/15. Polyisocyanate composition.

[In the general formulas (II) and (III), a plurality of R ²¹ and R ³¹ are each independently an organic group, and at least one of the plurality of R ²¹ and R ³¹ is a group represented by the general formula (V) Is a group represented by A plurality of R ²¹ and R ³¹ may be the same or different. R ³² is a residue obtained by removing one hydroxy group from a monovalent or higher alcohol. ]

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ] The polyisocyanate composition according to claim 10, further comprising a triisocyanate represented by the general formula (V) -1.

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ] The polyisocyanate compound represented by the general formula (II) and the general formula (IV), wherein the molar ratio between the isocyanurate structure and the uretdione structure is from 100 / 0.1 to 100/100. Polyisocyanate composition.

[In the general formulas (II) and (IV), a plurality of R ²¹ and R ⁴¹ are each independently an organic group, and at least one of the plurality of R ²¹ and R ⁴¹ is represented by the general formula (V). It is a group to be performed. A plurality of R ²¹ and R ⁴¹ may be the same or different. "

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ] The polyisocyanate composition according to claim 12, further comprising a triisocyanate represented by the general formula (V) -1.

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ] The polyisocyanate compound represented by general formula (II) seen including,
The ratio (V ^h / V ^p ) of the reaction rate (V ^p ) between the polyisocyanate composition and the primary alcohol to the reaction rate (V ^h ) between the polyisocyanate derived from hexamethylene diisocyanate and the primary alcohol , The polyisocyanate composition , which is 5 or more and less than 13 .

[In the general formula (II), R ²¹ is an organic group. At least one of the plurality of R ²¹ is a group represented by the general formula (V) or a group represented by the general formula (VI). A plurality of R ²¹ may be the same or different. ]

[In the general formula (V), a plurality of Y ¹ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms and containing an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond. ] The polyisocyanate composition according to claim 14 , further comprising a triisocyanate represented by the general formula (V) -1 or a diisocyanate represented by the general formula (VI) -1.

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

[In general formula (VI) -1, Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ester structure. ] A polyisocyanate composition containing a polyisocyanate compound represented by the general formula (III),
The isocyanate group contained in the polyisocyanate composition, allophanate structure, isocyanurate structure, uretdione structure, iminooxadiazinedione structure, urethane structure, and the total number of nitrogen elements contained in the burette structure included in the allophanate structure nitrogen element ^{(however, R 31,} R ³² excluding nitrogen element contained in) a polyisocyanate composition according to claim 1 number is 60% or less than 1.5%.

[In the general formula (III), R ³¹ is an organic group. At least one of the plurality of R ³¹ is a group represented by the general formula (V), and R ³² is a residue obtained by removing a hydroxyl group of a monohydric or higher alcohol. ]

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ] Wherein R ³² contained in the allophanate structure is a residue obtained by removing the divalent or more hydroxyl groups of the alcohol, polyisocyanate composition according to claim 16. Wherein R ³² contained in the allophanate structure is a residue obtained by removing one or more valent alcohol hydroxyl groups of 3 to 50 carbon atoms, polyisocyanate composition according to claim 16 or 17. The polyisocyanate composition according to claim 1, comprising a polyisocyanate compound represented by the general formula (III).

[In general formula (III), a plurality of R ³¹ are each independently an organic group, and at least one of the plurality of R ³¹ is a group represented by general formula (V) or a general formula (VI) Is a group represented by A plurality of R ³¹ may be the same or different. R ³² is a residue obtained by removing one hydroxy group from a monovalent or higher alcohol. ]

[In the general formula (V), a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester structure and / or an ether structure. A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A wavy line indicates a bond. ]

[In the general formula (VI), Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including an ester structure. A wavy line indicates a bond. ] When the molar ratios of the allophanate structure, uretdione structure, iminooxadiazinedione structure, isocyanurate structure, urethane structure, and buret structure are a, b, c, d, e, and f, the molar ratio of the allophanate structure ( The polyisocyanate composition according to claim 19 , wherein a / (a + b + c + d + e + f)) is 0.02 or more and 0.95 or less. The ratio (V ^h / V ^p ) of the reaction rate (V ^p ) between the polyisocyanate composition and the primary alcohol to the reaction rate (V ^h ) between the polyisocyanate derived from hexamethylene diisocyanate and the primary alcohol, The polyisocyanate composition according to claim 19, wherein the composition is 5 or more and less than 13. The polyisocyanate composition according to any one of claims 19 to 21 , further comprising a triisocyanate represented by the general formula (V) -1 or a diisocyanate represented by the general formula (VI) -1.

[In general formula (V) -1, a plurality of Y ¹ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may include an ester structure and / or an ether structure. . A plurality of Y ¹ may be the same or different. R ⁵¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]

[In general formula (VI) -1, Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ester structure. ] The isocyanate group of the polyisocyanate compound represented by the general formula (I), (II), (III) or (IV) contained in the polyisocyanate composition according to any one of claims 1 to 22. A blocked polyisocyanate composition at least partially protected by a blocking agent. The isocyanate group of the polyisocyanate compound represented by the general formula (I), (II), (III) or (IV) contained in the polyisocyanate composition according to any one of claims 1 to 23. A hydrophilic polyisocyanate composition having a hydrophilic group added to at least a part thereof. The polyisocyanate compound represented by the general formula (I), (II), (III) or (VI) contained in the blocked polyisocyanate composition according to claim 23 , wherein at least a part of the isocyanate group is hydrophilic. A hydrophilic polyisocyanate composition to which groups have been added. A coating composition comprising the polyisocyanate composition according to any one of claims 1 to 22 and a polyol. A coating composition comprising the blocked polyisocyanate composition according to claim 23 and a polyol. A coating composition comprising the hydrophilic polyisocyanate composition according to claim 24 or 25 and a polyol. A coating film obtained by curing the coating composition according to any one of claims 26 to 28 . An aqueous dispersion comprising water and the polyisocyanate composition according to any one of claims 16 to 19 dispersed in water. An aqueous dispersion comprising water and the blocked polyisocyanate composition according to claim 23 . An aqueous dispersion comprising water and the hydrophilic polyisocyanate composition according to claim 24 or 25 .